Pesticidal compositions and related methods

ABSTRACT

A process of applying a pesticidal composition to an area to control a pest, wherein the pesticidal composition comprises at least one compound selected from a compound of formula I, or any agriculturally acceptable salt thereof, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , Q, Z, L, L a , and x are as described herein. A method of controlling pests comprises applying the pesticidal composition near a population of pests.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a divisional of U.S. patent application Ser. No.14/517,590, filed Oct. 17, 2014 which claims the benefit of U.S.Provisional Patent Application Ser. No. 61/894,364, filed Oct. 22, 2013,the disclosures of which are hereby incorporated herein in theirentirety by this reference.

TECHNICAL FIELD

This disclosure relates to the field of compounds having pesticidalutility against pests in Phyla Nematoda, Arthropoda, and/or Mollusca,processes to produce such compounds and intermediates used in suchprocesses. These compounds may be used, for example, as nematicides,acaricides, pesticides, insecticides, miticides, and/or molluscicides.

BACKGROUND

Controlling pest populations is essential to human health, modernagriculture, food storage, and hygiene. There are more than ten thousandspecies of pests that cause losses in agriculture and the world-wideagricultural losses amount to billions of U.S. dollars each year.Accordingly, there exists a continuous need for new pesticides and formethods of producing and using such pesticides.

DETAILED DESCRIPTION Definitions

The examples given in the definitions are non-exhaustive and must not beconstrued as limiting the present disclosure. It is understood that asubstituent should comply with chemical bonding rules and stericcompatibility constraints in relation to the particular molecule towhich it is attached.

“Alkyl” means and includes an acyclic, saturated, branched or unbranchedhydrocarbon. Non-limiting examples may include methyl, ethyl, propyl,isopropyl, 1-butyl, 2-butyl, isobutyl, tert-butyl, pentyl,2-methylbutyl, 1,1-dimethylpropyl, hexyl, heptyl, octyl, nonyl, ordecyl.

“Cycloalkyl” means and includes a monocyclic or polycyclic saturatedhydrocarbon. Non-limiting examples may include cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, norbornyl,bicycle[2.2.2]octyl, or decahydronapthyl.

“Alkenyl” means and includes an acyclic, branched or unbranchedhydrocarbon containing at least one carbon-carbon double bond.Non-limiting examples may include ethenyl, propenyl, butenyl, pentenyl,hexenyl, heptenyl, octenyl, nonenyl, or decenyl.

“Cycloalkenyl” means and includes a monocyclic or polycyclic hydrocarboncontaining at least one carbon-carbon double bond. Non-limiting examplesmay include cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, orcyclodecenyl.

“Alkynyl” means and includes acyclic, branched or unbranched hydrocarboncontaining at least one carbon-carbon triple bond. Non-limiting examplesmay include ethynyl, propargyl, butynyl, pentynyl, hexynyl, heptynyl,octynyl, nonynyl, or decynyl.

“Cycloalkynyl” means and includes a monocyclic or polycyclic hydrocarboncontaining at least one carbon-carbon triple bond. Non-limiting examplesmay include cycloheptynyl, cyclooctynyl, or cyclodecynyl.

“Aryl” means and includes an aromatic compound with or without anysubstitution. Non-limiting examples may include phenyl or naphthyl.

“Alkoxy” means and includes an alkyl group containing at least onecarbon-oxygen single bond. Non-limiting examples may include methoxy,ethoxy, propoxy, butoxy, cyclopropoxy, cyclobutoxy, or cyclopentoxy.

“Alkenyloxy” means and includes an alkenyl containing at least onecarbon-oxygen single bond. Non-limiting examples may include allyloxy,butenyloxy, pentenyloxy, hexenyloxy, heptenyloxy, octenyloxy,nonenyloxy, or decenyloxy.

“Alkynyloxy” means and includes an alkynyl containing at least onecarbon-oxygen single bond. Non-limiting examples may includepentynyloxy, hexynyloxy, heptynyloxy, octynyloxy, nonynyloxy, ordecynyloxy.

“Cycloalkoxy” means and includes a cycloalkyl containing at least onecarbon-oxygen single bond. Non-limiting examples may includecyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy,cycloheptyloxy, cyclooctyloxy, cyclodecyloxy, nothomyloxy, orbicyclo[2.2.2]octyloxy.

“Cyclohaloalkyl” means and includes a monocyclic or polycyclic,saturated substituent comprising carbon, halogen, and hydrogen.Non-limiting examples may include 1-chlorocyclopropyl,1-chlorocyclobutyl, or 1-dichlorocyclopentyl.

“Cycloalkenyloxy” means and include a cycloalkenyl further consisting ofa carbon-oxygen single bond. Non-limiting examples may includecyclobutenyloxy, cyclopentenyloxy, cyclohexenyloxy, cycloheptenyloxy,cyclooctenyloxy, cyclodecenyloxy, norbornenyloxy, orbicyclo[2.2.2]octenyloxy.

“Alkylthio” means and includes an alkyl group containing at least onecarbon-sulfur single bond.

“Haloalkylthio” means and includes an alkyl group containing at leastone carbon-sulfur single bond and halogen atom.

“Halo” or “halogen” means and includes fluorine, chlorine, bromine, oriodine.

“Haloalkyl” means and includes an alkyl group substituted with at leastone halogen atom.

“Haloalkoxy” means and includes an alkoxy group substituted with atleast one halogen atom.

“Heteroatom” means and includes sulfur (S), oxygen (O), or nitrogen (N)atom.

“Heteroalkyl” means and includes an alkyl containing at least one sulfur(S), oxygen (O), or nitrogen (N) atom.

“Heterocyclyl” means a cyclic substituent that may be fully saturated,partially unsaturated, or fully unsaturated, where the cyclic structurecontains at least one carbon and at least one heteroatom, where saidheteroatom is nitrogen, sulfur, or oxygen. In the case of sulfur, thatatom can be in other oxidation states such as a sulfoxide and sulfone.Examples of aromatic heterocyclyls include, but are not limited to,benzofuranyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl,benzothienyl, benzothiazolyl, cinnolinyl, furanyl, imidazolyl,indazolyl, indolyl, isoindolyl, isoquinolinyl, isothiazolyl, isoxazolyl,oxadiazolyl, oxazolinyl, oxazolyl, phthalazinyl, pyrazinyl, pyrazolinyl,pyrazolyl, pyridazinyl, pyridyl, pyrimidinyl, pyrrolyl, quinazolinyl,quinolinyl, quinoxalinyl, tetrazolyl, thiazolinyl, thiazolyl, thienyl,triazinyl, and triazolyl. Examples of fully saturated heterocyclylsinclude, but are not limited to, piperazinyl, piperidinyl, morpholinyl,pyrrolidinyl, oxetanyl, tetrahydrofuranyl, tetrahydrothienyl andtetrahydropyranyl. Examples of partially unsaturated heterocyclylsinclude, but are not limited to, 1,2,3,4-tetrahydroquinolinyl,4,5-dihydro-oxazolyl, 4,5-dihydro-1H-pyrazolyl, 4,5-dihydro-isoxazolyl,and 2,3-dihydro-[1,3,4]-oxadiazolyl. Additional examples include thefollowing

“Pesticidally effective amount” means and includes an amount of activematerial that causes an adverse effect to at least one insect, whereinthe adverse effect may include deviations from natural development,killing, regulation, or the like.

“Control” or grammatical variations thereof means and includesregulating the number of living insects or regulating the number ofviable eggs of the insects.

“Synergistic effect” or grammatical variations thereof means andincludes a cooperative action encountered in a combination of two ormore active agents in which the combined activity of the two or moreactive agents exceeds the sum of the activity of each active agentalone.

Pesticidal Compounds

In one particular embodiment, a pesticidal composition comprises atleast one compound selected from compounds of formula I or anyagriculturally acceptable salt thereof:

wherein:

R₁, R₂, and R₄ are independently selected from hydrogen, F, Cl, Br, I,substituted or unsubstituted C₁-C₆ alkyl, or substituted orunsubstituted C₁-C₆ haloalkyl, wherein each said R₁, R₂, and R₄, whensubstituted, has one or more substituents selected from F, Cl, Br, I,CN, NO₂, C₁-C₆ alkyl, C₂-C₆ alkenyl, C₁-C₆ haloalkyl, C₃-C₁₀ cycloalkyl,or C₃-C₁₀ halocycloalkyl, (each of which that can be substituted, mayoptionally be substituted with R₁₀);

R₃ is selected from hydrogen, F, Cl, Br, I, CN, NO₂, substituted orunsubstituted C₁-C₆ alkyl, substituted or unsubstituted C₂-C₆ alkenyl,substituted or unsubstituted C₁-C₆ alkoxy, substituted or unsubstitutedC₃-C₁₀ cycloalkyl, substituted or unsubstituted C₁-C₆ haloalkyl,substituted or unsubstituted C₆-C₂₀ aryl, substituted or unsubstitutedC₁-C₂₀ heterocyclyl, OR₁₀, C(═X₁)R₁₀, C(═X₁)OR₁₀, C(═X₁)N(R₁₀)₂,N(R₁₀)₂, N(R₁₀)C(═X₁)R₁₀, SR₁₀, S(O)_(n)OR₁₀, or R₁₀S(O)_(n)R₁₀, whereineach said R₃, when substituted, has one or more substituents selectedfrom F, Cl, Br, I, CN, NO₂, C₁-C₆ alkyl, C₂-C₆ alkenyl, C₁-C₆ haloalkyl,C₂-C₆ haloalkenyl, C₁-C₆ haloalkyloxy, C₂-C₆ haloalkenyloxy, C₃-C₁₀cycloalkyl, C₃-C₁₀ cycloalkenyl, C₃-C₁₀ halocycloalkyl, C₃-C₁₀halocycloalkenyl, OR₁₀, S(O)_(n)OR₁₀, C₆-C₂₀ aryl, or C₁-C₂₀heterocyclyl, (each of which that can be substituted, may optionally besubstituted with R₁₀);

R₅ is selected from H, F, Cl, Br, I, CN, NO₂, substituted orunsubstituted C₁-C₆ alkyl, substituted or unsubstituted C₂-C₆ alkenyl,substituted or unsubstituted C₁-C₆ alkoxy, C₃-C₁₀ cycloalkyl,substituted or unsubstituted C₆-C₂₀ aryl, substituted or unsubstitutedC₁-C₂₀ heterocyclyl, OR₁₀, C(═X₁)R₁₀, C(═X₁)OR₁₀, C(═X₁)N(R₁₀)₂,N(R₁₀)₂, N(R₁₀)C(═X₁)R₁₀, S(O)_(n)R₁₀, S(O)_(n)OR₁₀, or R₁₀S(O)_(n)R₁₀,wherein each said R₅, when substituted, has one or more substituentsselected from F, Cl, Br, I, CN, NO₂, C₁-C₆ alkyl, C₂-C₆ alkenyl, C₁-C₆haloalkyl, C₂-C₆ haloalkenyl, C₁-C₆ haloalkyloxy, C₂-C₆ haloalkenyloxy,C₃-C₁₀ cycloalkyl, C₃-C₁₀ cycloalkenyl, C₃-C₁₀ halocycloalkyl, C₃-C₁₀halocycloalkenyl, OR₁₀, S(O)_(n)OR₁₀, C₆-C₂₀ aryl, or C₁-C₂₀heterocyclyl, (each of which that can be substituted, may optionally besubstituted with R₁₀);

R₆ is selected from H, F, Cl, Br, I, substituted or unsubstituted C₁-C₆alkyl, or C₁-C₆ haloalkyl, wherein each said R₆, when substituted, hasone or more substituents selected from F, Cl, Br, I, CN, NO₂, C₁-C₆alkyl, C₂-C₆ alkenyl, C₁-C₆ haloalkyl, C₂-C₆ haloalkenyl, C₁-C₆haloalkyloxy, C₂-C₆ haloalkenyloxy, C₃-C₁₀ cycloalkyl, C₃-C₁₀cycloalkenyl, C₃-C₁₀ halocycloalkyl, or C₃-C₁₀ halocycloalkenyl;

R₇ is selected from hydrogen, substituted or unsubstituted C₁-C₆ alkyl,substituted or unsubstituted C₂-C₆ alkenyl, substituted or unsubstitutedC₂-C₆ alkynyl, substituted or unsubstituted C₁-C₆ alkoxy, substituted orunsubstituted C₃-C₁₀ cycloalkyl, C₁-C₆ alkyl C₂-C₆ alkynyl (wherein thealkyl and alkynyl may independently be substituted or unsubstituted),substituted or unsubstituted C₆-C₂₀ aryl, substituted or unsubstitutedC₁-C₂₀ heterocyclyl, C₁-C₆ alkyl C₆-C₂₀ aryl (wherein the alkyl and arylmay independently be substituted or unsubstituted), C₁-C₆ alkyl-(C₃-C₁₀cyclohaloalkyl) wherein the alkyl and cyclohaloalkyl may independentlybe substituted or unsubstituted, or C₁-C₆ alkyl-(C₃-C₁₀ cycloalkyl)wherein the alkyl and cycloalkyl may independently be substituted orunsubstituted, wherein each said R₇, when substituted, has one or moresubstituents selected from F, Cl, Br, I, CN, NO₂, C₁-C₆ alkyl, C₂-C₆alkenyl, C₂-C₆ alkynyl, C₁-C₆ haloalkyl, C₂-C₆ haloalkenyl, C₁-C₆haloalkyloxy, C₂-C₆ haloalkenyloxy, C₃-C₁₀ cycloalkyl, C₃-C₁₀cycloalkenyl, C₃-C₁₀ halocycloalkyl, C₃-C₁₀ halocycloalkenyl, OR₁₀,S(O)_(n)OR₁₀, C₆-C₂₀ aryl, or C₁-C₂₀ heterocyclyl, R₁₀ aryl, (each ofwhich that can be substituted, may optionally be substituted with R₁₀);

R₈ is selected from substituted or unsubstituted C₁-C₆ alkyl,substituted or unsubstituted C₂-C₆ alkenyl, substituted or unsubstitutedC₁-C₆ alkoxy, substituted or unsubstituted C₃-C₁₀ cycloalkyl,substituted or unsubstituted C₃-C₁₀ halocycloalkyl substituted orunsubstituted C₃-C₁₀ cycloalkenyl, substituted or unsubstituted C₆-C₂₀aryl, or substituted or unsubstituted C₁-C₂₀ heterocyclyl,

wherein each said R₈, when substituted, has one or more substituentsselected from F, Cl, Br, I, CN, NO₂, substituted or unsubstituted C₁-C₆alkyl, substituted or unsubstituted C₂-C₆ alkenyl, substituted orunsubstituted C₁-C₆ haloalkyl, substituted or unsubstituted C₂-C₆haloalkenyl, substituted or unsubstituted C₁-C₆ haloalkyloxy,substituted or unsubstituted C₂-C₆ haloalkenyloxy, substituted orunsubstituted C₃-C₁₀ cycloalkyl, substituted or unsubstituted C₃-C₁₀cycloalkenyl, substituted or unsubstituted C₃-C₁₀ halocycloalkyl,substituted or unsubstituted C₃-C₁₀ halocycloalkenyl, oxo, OR₁₀,S(O)_(n)R₁₀, substituted or unsubstituted C₆-C₂₀ aryl, or substituted orunsubstituted C₁-C₂₀ heterocyclyl, (each of which, when substituted, issubstituted with R₁₀);

L is selected from a bond, R₉, O, S, N(R₉), N(R₉)C(═X₁), C(R₉)₂, orC(R₉)(R₁₁);

L_(a) is selected from R₉, OR₉, N(R₉)₂, N(R₉)(R₁₁), N(R₉)(OR₁₁),N(R₉)C(═X₁)R₉, N(R₉)C(═X₁)(R₁₁), C(R₉)₃, C(R₉)(R₁₁)(R₁₂), or SR₉;

optionally L and L_(a) is connected in a cyclic arrangement, which forms3-8 membered heterocycles or carbocycles including L and L_(a), whereinthe cyclic arrangement contains none or at least one of O, S, or Nheteroatoms, and the cyclic arrangement is unsubstituted or substituted,wherein when substituted, the cyclic arrangement has one or moresubstituents selected from F, Cl, Br, I, CN, NO₂, substituted orunsubstituted C₁-C₆ alkyl, substituted or unsubstituted C₂-C₆ alkenyl,substituted or unsubstituted C₂-C₆ alkynyl, substituted or unsubstitutedC₁-C₆ haloalkyl, substituted or unsubstituted C₂-C₆ haloalkenyl,substituted or unsubstituted C₁-C₆ haloalkyloxy, substituted orunsubstituted C₂-C₆ haloalkenyloxy, substituted or unsubstituted C₃-C₁₀cycloalkyl, substituted or unsubstituted C₃-C₁₀ cycloalkenyl,substituted or unsubstituted C₃-C₁₀ halocycloalkyl, substituted orunsubstituted C₃-C₁₀ halocycloalkenyl, N(R₉)S(O)₁R₁₁, oxo, OR₉,S(O)_(n)OR₉, R₉S(O)_(n)R₁₁, S(O)_(n)R₉, substituted or unsubstitutedC₆-C₂₀ aryl, or substituted or unsubstituted C₁-C₂₀ heterocyclyl (eachof which, when substituted, is substituted with R₁₀);

R₉, R₁₁, R₁₂, and R₁₃ are independently selected from hydrogen, CN, NO₂,substituted or unsubstituted C₁-C₆ alkyl, substituted or unsubstitutedC₂-C₆ alkenyl, substituted or unsubstituted C₁-C₆ alkoxy, substituted orunsubstituted C₃-C₁₀ cycloalkyl, substituted or unsubstituted C₃-C₁₀halocycloalkyl, substituted or unsubstituted C₃-C₁₀ cycloalkenyl,substituted or unsubstituted C₆-C₂₀ aryl, or substituted orunsubstituted C₁-C₂₀ heterocyclyl.

wherein each of said R₉, R₁₁, and R₁₂, when substituted, has one or moresubstituents selected from F, Cl, Br, I, CN, NO₂, substituted orunsubstituted C₁-C₆ alkyl, substituted or unsubstituted C₂-C₆ alkenyl,substituted or unsubstituted C₁-C₆ haloalkyl, substituted orunsubstituted C₂-C₆ haloalkenyl, substituted or unsubstituted C₁-C₆haloalkyloxy, substituted or unsubstituted C₂-C₆ haloalkenyloxy,substituted or unsubstituted C₃-C₁₀ cycloalkyl, substituted orunsubstituted C₃-C₁₀ cycloalkenyl, substituted or unsubstituted C₃-C₁₀halocycloalkyl, substituted or unsubstituted C₃-C₁₀ halocycloalkenyl,oxo, OR₁₀, C(═X₁)R₁₀, S(O)_(n)R₁₀, substituted or unsubstituted C₆-C₂₀aryl, or substituted or unsubstituted C₁-C₂₀ heterocyclyl, (each ofwhich, when substituted, is substituted with R₁₀);

R₁₀ is H, F, Cl, Br, I, CN, NO₂, substituted or unsubstituted C₁-C₆alkyl, substituted or unsubstituted C₂-C₆ alkenyl, substituted orunsubstituted C₁-C₆ alkoxy, substituted or unsubstituted C₂-C₆alkenyloxy, substituted or unsubstituted C₃-C₁₀ cycloalkyl, substitutedor unsubstituted C₃-C₁₀ cycloalkenyl, substituted or unsubstitutedC₆-C₂₀ aryl, substituted or unsubstituted C₁-C₂₀ heterocyclyl,substituted or unsubstituted S(O)_(n)C₁-C₆ alkyl, or substituted orunsubstituted N(C₁-C₆alkyl)₂,

wherein each said R₁₀, when substituted, has one or more substituentsselected from F, Cl, Br, I, CN, NO₂, C₁-C₆ alkyl, C₂-C₆ alkenyl, C₁-C₆haloalkyl, C₂-C₆ haloalkenyl, C₁-C₆ haloalkyloxy, C₂-C₆ haloalkenyloxy,C₃-C₁₀ cycloalkyl, C₃-C₁₀ cycloalkenyl, C₃-C₁₀ halocycloalkyl, C₃-C₁₀halocycloalkenyl, OC₁-C₆ alkyl, OC₁-C₆ haloalkyl, S(O)_(n)C₁-C₆alkyl,S(O)_(n)OC₁-C₆ alkyl, C₆-C₂₀ aryl, or C₁-C₂₀ heterocyclyl;

Q is (each independently) O or S;

Z is (each independently) O, S, CH₂, NR₁₃ or NOR₁₃;

X₁ is (each independently) O or S;

n is 0, 1, or 2; and

x is 0 or 1.

The compound of formula I, when R₇ is H, may exist in various isomericforms. Non-limiting examples of such isomeric forms may include, but arenot limited to, compounds IA, or IB as shown below.

In one embodiment, compounds of formula I may be prepared usingcarboxylic acids as shown in Scheme 1.

As shown in Scheme 1, compounds of formula I in which R₁, R₂, R₃, R₄,R₅, R₆, R₇, L, L_(a) and x are as previously defined may be preparedfrom the reaction of the corresponding1-(pyridin-3-yl)-1H-pyrazol-4-amine of formula 1-1 (prepared accordingto the U.S. Patent Publication No. 2012/0110702) and carboxylic acid1-2. The 1-(pyridin-3-yl)-1H-pyrazol-4-amine (1-1) may be coupled to acarboxylic acid (1-2) with a coupling reagent, such as1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC) ordicyclohexylcarbodiimide (DCC), in the presence of a base, such as4-dimethylaminopyridine (DMAP) or diisopropylethylamine (DIPEA), in apolar aprotic solvent, such as N,N-dimethylformamide (DMF),dichloromethane (CH₂Cl₂), or 1,2-dichloroethane (DCE), at a temperaturefrom about −10° C. to about 40° C. to produce compounds of formula I.

In another embodiment, compounds of formula I may be prepared using acidanhydride as shown in Scheme 2.

As shown in Scheme 2, compounds of formula I may be prepared from thereaction of the corresponding 1-(pyridin-3-yl)-1H-pyrazol-4-amine (1-1)and an acid anhydride (2-1). In step a of Scheme 2, the acid anhydride(2-1) may be generated from a carboxylic acid precursor (1-2) using areagent such as isobutyl chloroformate and a base, such as DIPEA, in apolar aprotic solvent, such as CH₂Cl₂, at a temperature from about −78°C. to about 30° C. In step b of Scheme 2, the1-(pyridin-3-yl)-1H-pyrazol-4-amine of formula 1-1 may be coupled withthe acid anhydride (2-1) in a polar aprotic solvent, such as CH₂Cl₂, ata temperature from about −78° C. to about 30° C., to give compounds offormula I.

In yet another embodiment, compounds of formula I may be prepared usingan acid chloride as shown in Scheme 3.

In step a of Scheme 3, the carboxylic acids of formula 1-2 may betreated with a reagent such as oxalyl chloride or thionyl chloride, inthe presence of an initiator, such as dimethylformamide, in an aproticsolvent, such as CH₂Cl₂, at a temperature from about −20° C. to about60° C. to give acid chlorides of the formula (3-1). In step b of Scheme3, the acid chloride (3-1) may then be coupled with a1-(pyridin-3-yl)-1H-pyrazol-4-amine of formula 1-1 in the presence of abase, such as diisopropylethylamine, and an aprotic solvent, such asdichloroethane, at a temperature from about −20° C. to about 60° C., toafford the compounds of formula I.

In one embodiment, compounds of formula 4-3 may be prepared as shown inScheme 4.

As shown in Scheme 4, compounds of formula 4-3 may be prepared from areaction of a corresponding 1-(pyridin-3-yl)-1H-pyrazol-4-amine (1-1)(prepared according to the U.S. Publication No. 2012/0110702) and aknown carboxylic acid (4-1) (Bioorganic & Medicinal Chemistry Letters,2008, 18, 4163). In step a of Scheme 4,1-(pyridin-3-yl)-1H-pyrazol-4-amine (1-1) may be coupled to a carboxylicacid (4-1) in a presence of a coupling reagent, such asn-propylphosphonic anhydride (T3P®), and a base, such as triethylamine,in a polar aprotic solvent, such as ethyl acetate (EtOAc), at atemperature from about −10° C. to about 80° C. to form compounds offormula 4-2. In step b of Scheme 4, the amide N—H group in compounds 4-2may be further reacted with a base, such as sodium hydride (NaH), in thepresence of a suitable electrophile, such as methyl iodide, in a polaraprotic solvent, such as DMF, at a temperature from about −30° C. toabout 30° C. to provide the products 4-3.

In one embodiment, compounds of formula 5-4 may be prepared as shown inScheme 5.

In step a of Scheme 5, 1-(pyridin-3-yl)-1H-pyrazol-4-amine of formula5-1 may be treated with a suitable electrophile, such as succinicanhydride, in a presence of an amine, such as triethylamine, and acatalyst, such as DMAP, in a polar aprotic solvent, such as DCE, at atemperature from about 0° C. to about 80° C. to produce compounds offormula 5-2. In step b of Scheme 5, compounds of formula 5-2 may betreated with a suitable amine of formula 5-3 (which may be in the formof an salt), in the presence of a coupling reagent, such asN,N′-dicyclohexylcarbodiimide (DCC) or1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDCI), anda base, such as DMAP, in a polar aprotic solvent, such as diethyl etheror CH₂Cl₂, at a temperature of about 0° C. to about 25° C. to providethe products 5-4.

In one embodiment, compounds of formula 6-5 may be prepared as shown inScheme 6.

In step a of Scheme 6, the N-Boc protected bis-heterocyclic amide offormula 6-1 may be treated with an acid, such as trifluoroacetic acid(TFA), in a polar aprotic solvent, such as CH₂Cl₂, at a temperature fromabout 0° C. to about 30° C. to yield bis-heterocyclic amine of formula6-2. In step b, the bis-heterocyclic amine (6-2) may be treated with anacid of formula 6-3, in the presence of a coupling reagent, such as DCCor EDCI, and a base, such as DMAP, in a solvent, such as diethyl etheror CH₂Cl₂, at a temperature from about 0° C. to about 25° C. to providethe products 6-5. Alternatively, as shown in step c, bis-heterocyclicamine (6-2) may be treated with an acyl chloride of formula 6-4 in thepresence of base, such as DMAP and/or pyridine, in a polar aproticsolvent, such as CH₂Cl₂, at a temperature from about 0° C. to about 30°C. to provide the products 6-5.

In one embodiment, compounds of formula 7-4 and 7-7 may be prepared asshown in Scheme 7.

In step a of Scheme 7, compounds of formula 7-1 may be treated withN-Boc protected compounds of formula 7-2, which may be pre-treated witha base, such as lithium bis(trimethylsilyl)amide (LiHMDS), in a polaraprotic solvent, such as tetrahydrofuran (THF), at a temperature fromabout −78° C. to about −60° C. to yield N-Boc protected bis-heterocyclicamide of formula 7-3. In step b, N-Boc protected bis-heterocyclic amideof formula 7-3 may then be treated with an acid, such as TFA, in a polaraprotic solvent, such as CH₂Cl₂, at a temperature from about 0° C. toabout 30° C. to yield compounds 7-4.

Alternatively, as shown in step c of Scheme 7, compounds of formula 7-1may be treated with N-silyl protected compounds of formula 7-5, whichmay be pre-treated with a base, such as n-butyllithium, in a polaraprotic solvent, such as THF, at a temperature from about −78° C. toabout −60° C. to yield N-silyl protected bis-heterocyclic amide offormula 7-6. In step d, compounds of formula 7-6 may be treated with afluoride source, such as tetrabutylammonium fluoride, in a polar aproticsolvent, such as THF, at a temperature from about 0° C. to about 30° C.,to yield compounds 7-4. In step e, compounds of formula 7-4 may betreated with a base, such as sodium hydride, and an alkylating reagent,such as 2,2,2-trifluoroethyl trifluromethanesulfonate, in a polaraprotic solvent, such as THF, at a temperature from about −30° C. toabout 40° C., to yield compounds 7-7.

In one embodiment, compounds of formula 8-3 may be prepared as shown inScheme 8.

In Scheme 8, compounds of formula 8-1 may be treated with a suitablebase, such as NaH, and sequentially treated with an electrophile R₉-LG(8-2), such as an methyl iodide, in which LG is a leaving group, in anaprotic solvent, such as DMF, at a temperature from about 0° C. to about30° C. to provide compounds of formula 8-3.

In one embodiment, compounds of formula 9-5 may be prepared as shown inScheme 9.

In step a of Scheme 9, 1-(pyridin-3-yl)-1H-pyrazol-4-amine of formula9-1 may be deprotonated with a base, such as LiHMDS, and acylated withan N-Boc protected imide of formula 9-2 in a polar aprotic solvent, suchas THF, at a temperature from about −78° C. to about 0° C. to yield anN-Boc protected bis-heterocyclic amide of formula 9-3.

In step b of Scheme 9, the N-Boc protected bis-heterocyclic amide (9-3)may be deprotected using an acid, such as TFA, in a polar aproticsolvent, such as CH₂Cl₂, at a temperature from about 0° C. to about 30°C. to yield bis-heterocyclic ammonium salt of formula 9-4, in which Y isa counter anion, such as trifluoroacetate.

In step c of Scheme 9, the bis-heterocyclic ammonium salt (9-4) may beacylated with an acid chloride, such as acetyl chloride, in a presenceof a base, such as triethylamine, in a polar aprotic solvent, such asCH₂Cl₂, at a temperature from about 0° C. to about 60° C. to provide theproducts 9-5.

In one embodiment, the oxime of formula 10-6 may be prepared as shown inScheme 10.

In step a of Scheme 10, 1-(pyridin-3-yl)-1H-pyrazol-4-amine of formula10-1 may be treated with an acid of formula 10-2, in a presence of acoupling reagent, such as EDC, and a base, such as DMAP, in a polaraprotic solvent, such as CH₂Cl₂, at a temperature from about −20° C. toabout 70° C. to afford bis-heterocyclic ketone of formula 10-4.Alternatively, as shown in step b, bis-heterocyclic ketone (10-4) may beprepared by reacting 1-(pyridin-3-yl)-1H-pyrazol-4-amine of formula 10-1with an acyl chloride of formula 10-3 in the presence of a base, such asDMAP, in a polar aprotic solvent, such as CH₂Cl₂. In step c,bis-heterocyclic ketone (10-4) may be reacted with a hydroxylamine offormula 10-5 or its hydrochloride salt, such as O-methylhydroxylaminehydrochloride or iso-propylhydroxylamine hydrochloride, in the presenceof a base, such as DIPEA, triethylamine, or pyridine, in a proticsolvent, such as ethanol (EtOH), at a temperature from about 25° C. toabout 100° C. to afford the bis-heterocyclic amide oxime of formula10-6.

In one embodiment, compounds of formula 11-8 may be prepared as shown inScheme 11.

In step a of Scheme 11, 1-(pyridin-3-yl)-1H-pyrazol-4-amine of formula11-1 may be reacted with an acid chloride of formula 11-2, where LG is aleaving group such as Cl, in the presence of a proton scavenger, such aspropylene oxide, DMAP or pyridine, and an aprotic solvent, such as DCE,at a temperature from about −20° C. to about 200° C. to afford compoundsof formula 11-3. In step b, the compounds of formula 11-3 may be treatedwith an alkyl amine of formula 11-4, such as methyl amine, in a proticsolvent, such as ethanol, at a temperature from about 25° C. to about150° C. to yield bis-heterocyclic amine of formula 11-5. In step c,bis-heterocyclic amine of formula 11-5 may be treated with an acylchloride of formula 11-6, such as acetyl chloride or ethylchloroformate, in the presence of a base, such as DMAP, DIPEA,triethylamine or pyridine, in an aprotic solvent, such as THF or CH₂Cl₂,at a temperature from about 0° C. to about 30° C. to yieldbis-heterocyclic amide of formula 11-8. Alternatively, as shown in stepd, bis-heterocyclic amine of formula 11-5 may be treated with acarboxylix acid of formula 11-7, in a presence of a coupling reagent,such as EDCI, and a base, such as DMAP, in a polar aprotic solvent, suchas CH₂Cl₂, at a temperature from about −20° C. to about 70° C. toprovide compounds of formula 11-8.

In one embodiment, compounds of formula 12-6 may be prepared as shown inScheme 12.

In step a of Scheme 12, 1-(pyridin-3-yl)-1H-pyrazol-4-amine of formula12-1 may be reacted with an acid chloride of formula 12-2 in thepresence of a base, such as DMAP, DIPEA, triethylamine or pyridine, inan aprotic solvent, such as THF or CH₂Cl₂, at a temperature from about0° C. to about 30° C. to afford bis-heterocyclic compounds of formula12-3. As shown in step b, treating the bis-heterocyclic compound offormula 12-3 with a base, such as aqueous 2M lithium hydroxide, in apolar solvent, such as methanol (MeOH), may afford the bis-heterocycliccompounds of formula 12-4. In step c, reacting the bis-heterocycliccompound of formula 12-4 with an acid chloride of formula 12-5 in apresence of a base, such as DMAP, DIPEA, triethylamine or pyridine, inan aprotic solvent, such as THF or CH₂Cl₂, at a temperature from about0° C. to about 30° C. may yield compounds of formula 12-6.

In one embodiment, compounds of formula 13-4 may be prepared as shown inScheme 13.

In step a of Scheme 13, compounds of formula 13-1 may be treated with anoxidant, such as ozone, in a polar solvent, such as CH₂Cl₂ and methanol,at a temperature from about −78° C. to about −40° C. to providecompounds of formula 13-2. In step b, compounds of formula 13-2 may betreated with a nucleophile, such as methylmagnesium bromide, in a polaraprotic solvent, such as THF, at a temperature from about −78° C. toabout −40° C. to provide compounds of formula 13-3. In step c, compoundsof formula 13-3 may be treated with an oxidant, such as Dess-Martinperiodinane, in a polar aprotic solvent, such as CH₂Cl₂, at atemperature of from about −30° C. to about 30° C. to provide compoundsof formula 13-4.

Pesticidally Acceptable Acid Addition Salts, Salt Derivatives, Solvates,Ester Derivatives, Polymorphs, Isotopes, Radionuclides and Stereoisomers

In some embodiments, the compound of formula I may be formulated intopesticidally acceptable acid addition salts. By way of a non-limitingexample, an amine function can form salts with hydrochloric,hydrobromic, sulfuric, phosphoric, acetic, benzoic, citric, malonic,salicylic, malic, fumaric, oxalic, succinic, tartaric, lactic, gluconic,ascorbic, maleic, aspartic, benzenesulfonic, methanesulfonic,ethanesulfonic, hydroxymethanesulfonic, hydroxyethanesulfonic, andtrifluoroacetic acids. Additionally, by way of a non-limiting example,an acid function can form salts including those derived from alkali oralkaline earth metals and those derived from ammonia and amines.Examples of preferred cations include sodium, potassium, and magnesium.

In some embodiments, the compound of formula I may be formulated intosalt derivatives. By way of a non-limiting example, a salt derivativecan be prepared by contacting a free base with a sufficient amount ofthe desired acid to produce a salt. A free base may be regenerated bytreating the salt with a suitable dilute aqueous base solution such asdilute aqueous sodium hydroxide (NaOH), potassium carbonate, ammonia,and sodium bicarbonate. As an example, in many cases, a pesticide, suchas 2,4-D, is made more water-soluble by converting it to itsdimethylamine salt.

In further embodiments, the compound of formula I may be formulated intostable complexes with a solvent, such that the complex remains intactafter the non-complexed solvent is removed. These complexes are oftenreferred to as “solvates.” However, it is particularly desirable to formstable hydrates with water as the solvent.

In some embodiments, the compound of formula I may be made into esterderivatives. These ester derivatives can then be applied in the samemanner as the invention disclosed in this document is applied.

In some embodiments, the compound of formula I be made as variouscrystal polymorphs. Polymorphism is important in the development ofagrochemicals since different crystal polymorphs or structures of thesame molecule can have vastly different physical properties andbiological performances.

In further embodiments, the compound of formula I may be made withdifferent isotopes. Of particular importance are molecules having ²H(also known as deuterium) in place of ¹H.

In some embodiments, the compound of formula I may be made withdifferent radionuclides. Of particular importance are molecules having¹³C or ¹⁴C.

In some embodiments, the of formula I may exist as one or morestereoisomers. Thus, certain molecules can be produced as racemicmixtures. It will be appreciated by those skilled in the art that onestereoisomer may be more active than the other stereoisomers Individualstereoisomers may be obtained by known selective synthetic procedures,by conventional synthetic procedures using resolved starting materials,or by conventional resolution procedures. Certain molecules disclosed inthis document can exist as two or more isomers. The various isomersinclude geometric isomers, diastereomers, and enantiomers. Thus, themolecules disclosed in this document include geometric isomers, racemicmixtures, individual stereoisomers, and optically active mixtures. Itwill be appreciated by those skilled in the art that one isomer may bemore active than the others. The structures disclosed in the presentdisclosure are drawn in only one geometric form for clarity, but areintended to represent all geometric forms of the molecule.

Pesticidal Compositions

In one particular embodiment, a pesticidal composition comprises atleast one compounds selected from a compound of formula I or anyagriculturally acceptable salt thereof.

In some embodiments, a pesticidal composition comprises at least onecompounds selected from a compound of formula I, or any agriculturallyacceptable salt thereof, and a phytologically-acceptable inert carrier(e.g., solid carrier, or liquid carrier).

In one embodiment, the pesticidal composition may further comprise atleast one additive selected from surfactant, a stabilizer, an emeticagent, a disintegrating agent, an antifoaming agent, a wetting agent, adispersing agent, a binding agent, dyes, or fillers.

In some embodiments, the pesticidal compositions may be in the form ofsolid. Non-limiting examples of the solid forms may include power, dustor granular formulations.

In other embodiments, the pesticidal compositions may be in the form ofliquid formulation Examples of the liquid forms may include, but notlimited to, dispersion, suspension, emulsion or solution in appropriateliquid carrier.

In further embodiments, the pesticidal compositions may be in the formof liquid dispersion, wherein the compound of formula I may be dispersedin water or other agriculturally suitable liquid carrier.

In yet further embodiments, the pesticidal compositions may be in theform of solution in an appropriate organic solvent. In one embodiment,the spray oils, which are widely used in agricultural chemistry, may beused as an organic solvent for the pesticidal compositions.

The pesticidal composition may be used in conjunction (such as, in acompositional mixture, or a simultaneous or sequential application) withone or more compounds having acaricidal, algicidal, avicidal,bactericidal, fungicidal, herbicidal, insecticidal, molluscicidal,nematicidal, rodenticidal, and/or virucidal properties.

Furthermore, the pesticidal composition may be used in conjunction (suchas, in a compositional mixture, or a simultaneous or sequentialapplication) with one or more compounds that are antifeedants, birdrepellents, chemosterilants, herbicide safeners, insect attractants,insect repellents, mammal repellents, mating disrupters, plantactivators, plant growth regulators, and/or synergists.

Insecticides

Non-limiting examples of insecticides that may be used in combinationwith the compound of formula I may include 1,2-dichloropropane,abamectin, acephate, acetamiprid, acethion, acetoprole, acrinathrin,acrylonitrile, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin,allosamidin, allyxycarb, alpha-cypermethrin, alpha-ecdysone,α/p/ω-endosulfan, amidithion, aminocarb, amiton, amiton oxalate, amitmz,anabasine, athidathion, azadirachtin, azamethiphos, azinphos-ethyl,azinphos-methyl, azothoate, barium hexafluorosilicate, barthrin,bendiocarb, benfumcarb, bensultap, beta-cyfluthrin, beta-cypermethrin,bifenthrin, bioallethrin, bioethanomethrin, biopermethrin, bistrifluron,borax, boric acid, bromfenvinfos, bromocyclen, bromo-DDT, bromophos,bromophos-ethyl, bufencarb, buprofezin, butacarb, butathiofos,butocarboxim, butonate, butoxycarboxim, cadusafos, calcium arsenate,calcium polysulfide, camphechlor, carbanolate, carbaryl, carbofumn,carbon disulfide, carbon tetrachloride, cathophenothion, carbosulfan,cartap, cartap hydrochloride, chlorantraniliprole, chlorbicyclen,chlordane, chlordecone, chlordimeform, chlordimeform hydrochloride,chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron,chlormephos, chloroform, chloropicrin, chlorphoxim, chlorprazophos,chlorpyrifos, chlorpyrifos-methyl, chlorthiophos, chromafenozide,cinerin I, cinerin II, cinerins, cismethrin, cloethocarb, closantel,clothianidin, copper acetoarsenite, copper arsenate, copper naphthenate,copper oleate, coumaphos, coumithoate, crotamiton, crotoxyphos,crufomate, cryolite, cyanofenphos, cyanophos, cyanthoate,cyantraniliprole, cyclethrin, cycloprothrin, cyfluthrin, cyhalothrin,cypermethrin, cyphenothrin, cyromazine, cythioate, DDT, decarbofuran,deltamethrin, demephion, demephion-O, demephion-S, demeton,demeton-methyl, demeton-O, demeton-O-methyl, demeton-S,demeton-S-methyl, demeton-S-methylsulphon, diafenthiuron, dialifos,diatomaceous earth, diazinon, dicapthon, dichlofenthion, dichlorvos,dicresyl, dicrotophos, dicyclanil, dieldrin, diflubenzuron, dilor,dimefluthrin, dimefox, dimetan, dimethoate, dimethrin, dimethylvinphos,dimetilan, dinex, dinex-diclexine, dinoprop, dinosam, dinotefuran,diofenolan, dioxabenzofos, dioxacarb, dioxathion, disulfoton,dithicrofos, d-limonene, DNOC, DNOC-ammonium, DNOC-potassium,DNOC-sodium, doramectin, ecdysterone, emamectin, emamectin benzoate,EMPC, empenthrin, endosulfan, endothion, endrin, EPN, epofenonane,eprinomectin, esdépalléthrine, esfenvalerate, etaphos, ethiofencarb,ethion, ethiprole, ethoate-methyl, ethoprophos, ethyl formate,ethyl-DDD, ethylene dibromide, ethylene dichloride, ethylene oxide,etofenprox, etrimfos, EXD, famphur, fenamiphos, fenazaflor,fenchlorphos, fenethacarb, fenfluthrin, fenitrothion, fenobucarb,fenoxacrim, fenoxycarb, fenpirithrin, fenpropathrin, fensulfothion,fenthion, fenthion-ethyl, fenvalemte, fipronil, flonicamid,flubendiamide (additionally resolved isomers thereof), flucofuron,flucycloxuron, flucythrinate, flufenerim, flufenoxuron, flufenprox,fluvalinate, fonofos, formetanate, formetanate hydrochloride,formothion, formparanate, formparanate hydrochloride, fosmethilan,fospimte, fosthietan, fufenozide, fumthiocarb, furethrin,gαmmα-cyhalothrin, gamma-HCH, halfenprox, halofenozide, HCH, HEOD,heptachlor, heptenophos, heterophos, hexaflumuron, HHDN, hydramethylnon,hydrogen cyanide, hydroprene, hyquincarb, imidacloprid, imiprothrin,indoxacarb, iodomethane, IPSP, isazofos, isobenzan, isocathophos,isodrin, isofenphos, isofenphos-methyl, isoprocarb, isoprothiolane,isothioate, isoxathion, ivermectin, jasmolin I, jasmolin II, jodfenphos,juvenile hormone I, juvenile hormone II, juvenile hormone III, kelevan,kinoprene, lambda-cyhalothrin, lead arsenate, lepimectin, leptophos,lindane, lirimfos, lufenuron, lythidathion, malathion, malonoben,mazidox, mecarbam, mecarphon, menazon, meperfluthrin, mephosfolan,mercurous chloride, mesulfenfos, metaflumizone, methacrifos,methamidophos, methidathion, methiocarb, methocrotophos, methomyl,methoprene, methothrin, methoxychlor, methoxyfenozide, methyl bromide,methyl isothiocyanate, methylchloroform, methylene chloride,metofluthrin, metolcarb, metoxadiazone, mevinphos, mexacathate,milbemectin, milbemycin oxime, mipafox, mirex, molosultap,monocrotophos, monomehypo, monosultap, morphothion, moxidectin,naftalofos, naled, naphthalene, nicotine, nifluridide, nitenpyram,nithiazine, nitrilacarb, novaluron, noviflumuron, omethoate, oxamyl,oxydemeton-methyl, oxydeprofos, oxydisulfoton, para-dichlorobenzene,parathion, parathion-methyl, penfluron, pentachlorophenol, permethrin,phenkapton, phenothrin, phenthoate, phorate, phosalone, phosfolan,phosmet, phosnichlor, phosphamidon, phosphine, phoxim, phoxim-methyl,pirimetaphos, pirimicarb, pirimiphos-ethyl, pirimiphos-methyl, potassiumarsenite, potassium thiocyanate, pp′-DDT, prallethrin, precocene I,precocene II, precocene III, primidophos, profenofos, profluralin,profluthrin, promacyl, promecarb, propaphos, propetamphos, propoxur,prothidathion, prothiofos, prothoate, protrifenbute, pymetrozine,pyraclofos, pyrafluprole, pyrazophos, pyresmethrin, pyrethrin I,pyrethrin II, pyrethrins, pyridaben, pyridalyl, pyridaphenthion,pyrifluquinazon, pyrimidifen, pyrimitate, pyriprole, pyriproxyfen,quassia, quinalphos, quinalphos-methyl, quinothion, rafoxanide,resmethrin, rotenone, ryania, sabadilla, schradan, selamectin,silafluofen, silica gel, sodium arsenite, sodium fluoride, sodiumhexafluorosilicate, sodium thiocyanate, sophamide, spinetoram, spinosad,spiromesifen, spirotetramat, sulcofuron, sulcofuron-sodium, sulflummid,sulfotep, sulfoxaflor, sulfuryl fluoride, sulprofos, tau-fluvalinate,tazimcarb, TDE, tebufenozide, tebufenpyrad, tebupirimfos, teflubenzuron,tefluthrin, temephos, TEPP, terallethrin, terbufos, tetrachloroethane,tetrachlorvinphos, tetramethrin, tetramethylfluthrin, Λeto-cypermethrin,thiacloprid, thiamethoxam, thicrofos, thiocarboxime, thiocyclam,thiocyclam oxalate, thiodicarb, thiofanox, thiometon, thiosultap,thiosultap-disodium, thiosultap-monosodium, thuringiensin, tolfenpyrad,tralomethrin, tmnsfluthrin, tmnspermethrin, triamthene, triazamate,triazophos, trichlorfon, trichlormetaphos-3, trichloronat, trifenofos,triflumuron, trimethacarb, triprene, vamidothion, vaniliprole, XMC,xylylcarb, zeta-cypermethrin, or zolaprofos.

Acaricides

Non-limiting examples of acaricides that may be used in combination withthe compound of formula I may include acequinocyl, amidoflumet, arsenousoxide, azobenzene, azocyclotin, benomyl, benoxafos, benzoximate, benzylbenzoate, bifenazate, binapacryl, bromopropylate, chinomethionat,chlothenside, chlorfenethol, chlorfenson, chlorfensulphide,chlorobenzilate, chloromebuform, chloromethiuron, chloropropylate,clofentezine, cyenopyrafen, cyflumetofen, cyhexatin, dichlofluanid,dicofol, dienochlor, diflovidazin, dinobuton, dinocap, dinocap-4,dinocap-6, dinocton, dinopenton, dinosulfon, dinotelbon, diphenylsulfone, disulfiram, dofenapyn, etoxazole, fenazaquin, fenbutatin oxide,fenothiocarb, fenpyroximate, fenson, fentrifanil, fluacrypyrim,fluazuron, flubenzimine, fluenetil, flumethrin, fluorbenside,hexythiazox, mesulfen, MNAF, nikkomycins, proclonol, propargite,quintiofos, spirodiclofen, sulfiram, sulfur, tetradifon, tetranactin,tetrasul, or thioquinox.

Nematicides

Non-limiting examples of nematicides that may be used in combinationwith the compound of formula I may include 1,3-dichloropropene,benclothiaz, dazomet, dazomet-sodium, DBCP, DCIP, diamidafos,fluensulfone, fosthiazate, furfural, imicyafos, isamidofos, isazofos,metam, metam-ammonium, metam-potassium, metam-sodium, phosphocarb, orthionazin.

Fungicides

Non-limiting examples of fungicides that may be used in combination withthe compound of formula I may include (3-ethoxypropyl)mercury bromide,2-methoxyethylmercury chloride, 2-phenylphenol, 8-hydroxyquinolinesulfate, 8-phenylmercurioxyquinoline, acibenzolar, acibenzolar-S-methyl,acypetacs, acypetacs-copper, acypetacs-zinc, aldimorph, allyl alcohol,ametoctradin, amisulbrom, ampropylfos, anilazine, aureofungin,azaconazole, azithiram, azoxystrobin, barium polysulfide, benalaxyl,benalaxyl-M, benodanil, benomyl, benquinox, bentaluron, benthiavalicarb,benthiavalicarb-isopropyl, benzalkonium chloride, benzamacril,benzamacril-isobutyl, benzamorf, benzohydroxamic acid, bethoxazin,binapacryl, biphenyl, bitertanol, bithionol, bixafen, blasticidin-S,Bordeaux mixture, boscalid, bromuconazole, bupirimate, Burgundy mixture,buthiobate, butylamine, calcium polysulfide, captafol, captan,carbamorph, carbendazim, carboxin, carpropamid, carvone, Cheshuntmixture, chinomethionat, chlobenthiazone, chloraniformethan, chloranil,chlorfenazole, chlorodinitronaphthalene, chloroneb, chloropicrin,chlorothalonil, chlorquinox, chlozolinate, climbazole, clotrimazole,copper acetate, copper carbonate, basic, copper hydroxide, coppernaphthenate, copper oleate, copper oxychloride, copper silicate, coppersulfate, copper zinc chromate, cresol, cufraneb, cuprobam, cuprousoxide, cyazofamid, cyclafuramid, cycloheximide, cyflufenamid, cymoxanil,cypendazole, cyproconazole, cyprodinil, dazomet, dazomet-sodium, DBCP,debacarb, decafentin, dehydroacetic acid, dichlofluanid, dichlone,dichlorophen, dichlozoline, diclobutrazol, diclocymet, diclomezine,diclomezine-sodium, dicloran, diethofencarb, diethyl pyrocarbonate,difenoconazole, diflumetorim, dimethirimol, dimethomorph, dimoxystrobin,diniconazole, diniconazole-M, dinobuton, dinocap, dinocap-4, dinocap-6,dinocton, dinopenton, dinosulfon, dinoterbon, diphenylamine,dipyrithione, disulfiram, ditalimfos, dithianon, DNOC, DNOC-ammonium,DNOC-potassium, DNOC-sodium, dodemorph, dodemorph acetate, dodemorphbenzoate, dodicin, dodicin-sodium, dodine, drazoxolon, edifenphos,epoxiconazole, etaconazole, etem, ethaboxam, ethirimol, ethoxyquin,ethylmercury 2,3-dihydroxypropyl mercaptide, ethylmercury acetate,ethylmercury bromide, ethylmercury chloride, ethylmercury phosphate,etridiazole, famoxadone, fenamidone, fenaminosulf, fenapanil, fenarimol,fenbuconazole, fenfuram, fenhexamid, fenitropan, fenoxanil, fenpiclonil,fenpropidin, fenpropimorph, fentin, fentin chloride, fentin hydroxide,ferbam, ferimzone, fluazinam, fludioxonil, flumetover, flumorph,fluopicolide, fluopyram, fluoroimide, fluotrimazole, fluoxastrobin,fluquinconazole, flusilazole, flusulfamide, flutianil, flutolanil,flutriafol, fluxapyroxad, folpet, formaldehyde, fosetyl,fosetyl-aluminium, fuberidazole, furalaxyl, furametpyr, furcarbanil,furconazole, furconazole-cis, furfural, furmecyclox, furophanate,glyodin, griseofulvin, guazatine, halacrinate, hexachlorobenzene,hexachlorobutadiene, hexaconazole, hexylthiofos, hydrargaphen,hymexazol, imazalil, imazalil nitrate, imazalil sulfate, imibenconazole,iminoctadine, iminoctadine triacetate, iminoctadine trialbesilate,iodomethane, ipconazole, iprobenfos, iprodione, iprovalicarb,isoprothiolane, isopyrazam, isotianil, isovaledione, kasugamycin,kresoxim-methyl, mancopper, mancozeb, mandipropamid, maneb, mebenil,mecarbinzid, mepanipyrim, mepronil, meptyldinocap, mercuric chloride,mercuric oxide, mercurous chloride, metalaxyl, metalaxyl-M, metam,metam-ammonium, metam-potassium, metam-sodium, metazoxolon, metconazole,methasulfocarb, methfuroxam, methyl bromide, methyl isothiocyanate,methylmercury benzoate, methylmercury dicyandiamide, methylmercurypentachlorophenoxide, metiram, metominostrobin, metrafenone,metsulfovax, milneb, myclobutanil, myclozolin,N-(ethylmercury)-p-toluenesulphonanilide, nabam, natamycin,nitrostyrene, nitrothal-isopropyl, nuarimol, OCH, octhilinone, ofurace,orysastrobin, oxadixyl, oxine-copper, oxpoconazole, oxpoconazolefumarate, oxycarboxin, pefurazoate, penconazole, pencycuron, penflufen,pentachlorophenol, penthiopyrad, phenylmercuriurea, phenylmercuryacetate, phenylmercury chloride, phenylmercury derivative ofpyrocatechol, phenylmercury nitrate, phenylmercury salicylate,phosdiphen, phthalide, picoxystrobin, piperalin, polycarbamate,polyoxins, polyoxorim, polyoxorim-zinc, potassium azide, potassiumpolysulfide, potassium thiocyanate, probenazole, prochloraz,procymidone, propamocarb, propamocarb hydrochloride, propiconazole,propineb, proquinazid, prothiocarb, prothiocarb hydrochloride,prothioconazole, pymcarbolid, pyraclostrobin, pyraclostrobin,pyrametostrobin, pyraoxystrobin, pyrazophos, pyribencarb, pyridinitril,pyrifenox, pyrimethanil, pyriofenone, pyroquilon, pyroxychlor,pyroxyfur, quinacetol, quinacetol sulfate, quinazamid, quinconazole,quinoxyfen, quintozene, rabenzazole, salicylanilide, sedaxane,silthiofam, simeconazole, sodium azide, sodium orthophenylphenoxide,sodium pentachlorophenoxide, sodium polysulfide, spiroxamine,streptomycin, sulfur, sultropen, TCMTB, tebuconazole, tebufloquin,tecloftalam, tecnazene, tecoram, tetraconazole, thiabendazole,thiadifluor, thicyofen, thifluzamide, thiochlorfenphim, thiomersal,thiophanate, thiophanate-methyl, thioquinox, thiram, tiadinil, tioxymid,tolclofos-methyl, tolylfluanid, tolylmercury acetate, triadimefon,triadimenol, triamiphos, triarimol, triazbutil, triazoxide, tributyltinoxide, trichlamide, tricyclazole, tridemorph, trifloxystrobin,triflumizole, triforine, triticonazole, uniconazole, uniconazole-P,validamycin, valifenalate, vinclozolin, zarilamid, zinc naphthenate,zineb, ziram, or zoxamide.

Herbicides

Non-limiting examples of herbicides that may be used in combination thecompound of formula I may include 2,3,6-TBA, 2,3,6-TBA-dimethylammonium,2,3,6-TBA-sodium, 2,4,5-T, 2,4,5-T-2-butoxypropyl, 2,4,5-T-2-ethylhexyl,2,4,5-T-3-butoxypropyl, 2,4,5-TB, 2,4,5-T-butometyl, 2,4,5-T-butotyl,2,4,5-T-butyl, 2,4,5-T-isobutyl, 2,4,5-T-isoctyl, 2,4,5-T-isopropyl,2,4,5-T-methyl, 2,4,5-T-pentyl, 2,4,5-T-sodium,2,4,5-T-triethylammonium, 2,4,5-T-trolamine, 2,4-D,2,4-D-2-butoxypropyl, 2,4-D-2-ethylhexyl, 2,4-D-3-butoxypropyl,2,4-D-ammonium, 2,4-DB, 2,4-DB-butyl, 2,4-DB-dimethylammonium,2,4-DB-isoctyl, 2,4-DB-potassium, 2,4-DB-sodium, 2,4-D-butotyl,2,4-D-butyl, 2,4-D-diethylammonium, 2,4-D-dimethylammonium,2,4-D-diolamine, 2,4-D-dodecylammonium, 2,4-DEB, 2,4-DEP, 2,4-D-ethyl,2,4-D-heptylammonium, 2,4-D-isobutyl, 2,4-D-isoctyl, 2,4-D-isopropyl,2,4-D-isopropylammonium, 2,4-D-lithium, 2,4-D-meptyl, 2,4-D-methyl,2,4-D-octyl, 2,4-D-pentyl, 2,4-D-potassium, 2,4-D-propyl, 2,4-D-sodium,2,4-D-tefuryl, 2,4-D-tetradecylammonium, 2,4-D-triethylammonium,2,4-D-tris(2-hydroxypropyl)ammonium, 2,4-D-trolamine, 3,4-DA, 3,4-DB,3,4-DP, 4-CPA, 4-CPB, 4-CPP, acetochlor, acifluorfen,acifluorfen-methyl, acifluorfen-sodium, aclonifen, acrolein, alachlor,allidochlor, alloxydim, alloxydim-sodium, allyl alcohol, alorac,ametridione, ametryn, amibuzin, amicarbazone, amidosulfuron,aminocyclopymchlor, aminocyclopyrachlor-methyl,aminocyclopymchlor-potassium, aminopyralid, aminopyralid-potassium,aminopyralid-tris(2-hydroxypropyl)ammonium, amiprofos-methyl, amitrole,ammonium sulfamate, anilofos, anisuron, asulam, asulam-potassium,asulam-sodium, atraton, atrazine, azafenidin, azimsulfuron, aziprotryne,bathan, BCPC, beflubutamid, benazolin, benazolin-dimethylammonium,benazolin-ethyl, benazolin-potassium, bencathazone, benfluralin,benfuresate, bensulfuron, bensulfuron-methyl, bensulide, bentazone,bentazone-sodium, benzadox, benzadox-ammonium, benzfendizone, benzipram,benzobicyclon, benzofenap, benzofluor, benzoylprop, benzoylprop-ethyl,benzthiazuron, bicyclopyrone, bifenox, bilanafos, bilanafos-sodium,bispyribac, bispyribac-sodium, borax, bromacil, bromacil-lithium,bromacil-sodium, bromobonil, bromobutide, bromofenoxim, bromoxynil,bromoxynil butyrate, bromoxynil heptanoate, bromoxynil octanoate,bromoxynil-potassium, brompyrazon, butachlor, butafenacil, butamifos,butenachlor, buthidazole, buthiuron, butmlin, butroxydim, buturon,butylate, cacodylic acid, cafenstrole, calcium chlorate, calciumcyanamide, cambendichlor, cathasulam, cathetamide, carboxazole,carfentrazone, carfentrazone-ethyl, CDEA, CEPC, chlomethoxyfen,chloramben, chloramben-ammonium, chloramben-diolamine,chloramben-methyl, chloramben-methylammonium, chloramben-sodium,chloranocryl, chlorazifop, chlorazifop-propargyl, chlorazine,chlothromuron, chlothufam, chloreturon, chlorfenac, chlorfenac-sodium,chlorfenprop, chlorfenprop-methyl, chlorflurazole, chlorflurenol,chlorflurenol-methyl, chloridazon, chlorimuron, chlorimuron-ethyl,chlornitrofen, chloropon, chlorotoluron, chloroxuron, chloroxynil,chlorprocath, chlorpropham, chlorsulfuron, chlorthal,chlorthal-dimethyl, chlorthal-monomethyl, chlorthiamid, cinidon-ethyl,cinmethylin, cinosulfuron, cisanilide, clethodim, cliodinate,clodinafop, clodinafop-propargyl, clofop, clofop-isobutyl, clomazone,clomeprop, cloprop, cloproxydim, clopyralid, clopyralid-methyl,clopyralid-olamine, clopyralid-potassium,clopyralid-tris(2-hydroxypropyl)ammonium, cloransulam,cloransulam-methyl, CMA, copper sulfate, CPMF, CPPC, credazine, cresol,cumyluron, cyanamide, cyanatryn, cyanazine, cycloate, cyclosulfamuron,cycloxydim, cycluron, cyhalofop, cyhalofop-butyl, cyperquat, cyperquatchloride, cyprazine, cyprazole, cypromid, daimuron, dalapon,dalapon-calcium, dalapon-magnesium, dalapon-sodium, dazomet,dazomet-sodium, delachlor, desmedipham, desmetlyn, di-allate, dicamba,dicamba-dimethylammonium, dicamba-diolamine, dicamba-isopropylammonium,dicamba-methyl, dicamba-olamine, dicamba-potassium, dicamba-sodium,dicamba-trolamine, dichlobenil, dichloralurea, dichlormate, dichlorprop,dichlorprop-2-ethylhexyl, dichlorprop-butotyl,dichlorprop-dimethylammonium, dichlorprop-ethylammonium,dichlorprop-isoctyl, dichlorprop-methyl, dichlorprop-P,dichlorprop-P-dimethylammonium, dichlorprop-potassium,dichlorprop-sodium, diclofop, diclofop-methyl, diclosulam, diethamquat,diethamquat dichloride, diethatyl, diethatyl-ethyl, difenopenten,difenopenten-ethyl, difenoxuron, difenzoquat, difenzoquat metilsulfate,diflufenican, diflufenzopyr, diflufenzopyr-sodium, dimefuron,dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P,dimexano, dimidazon, dinitramine, dinofenate, dinoprop, dinosam,dinoseb, dinoseb acetate, dinoseb-ammonium, dinoseb-diolamine,dinoseb-sodium, dinoseb-trolamine, dinoteth, dinoteth acetate,diphacinone-sodium, diphenamid, dipropetryn, diquat, diquat dibromide,disul, disul-sodium, dithiopyr, diuron, DMPA, DNOC, DNOC-ammonium,DNOC-potassium, DNOC-sodium, DSMA, EBEP, eglinazine, eglinazine-ethyl,endothal, endothal-diammonium, endothal-dipotassium, endothal-disodium,epronaz, EPTC, ethon, esprocath, ethalfluralin, ethametsulfuron,ethametsulfuron-methyl, ethidimuron, ethiolate, ethofumesate, ethoxyfen,ethoxyfen-ethyl, ethoxysulfuron, etinofen, etnipromid, etobenzanid, EXD,fenasulam, fenoprop, fenoprop-3-butoxypropyl, fenoprop-butometyl,fenoprop-butotyl, fenoprop-butyl, fenoprop-isoctyl, fenoprop-methyl,fenoprop-potassium, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P,fenoxaprop-P-ethyl, fenoxasulfone, fenteracol, fenthiaprop,fenthiaprop-ethyl, fentrazamide, fenuron, fenuron TCA, ferrous sulfate,flamprop, flamprop-isopropyl, flamprop-M, flamprop-methyl,flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, florasulam,fluazifop, fluazifop-butyl, fluazifop-methyl, fluazifop-P,fluazifop-P-butyl, fluazolate, flucathazone, flucathazone-sodium,flucetosulfuron, fluchloralin, flufenacet, flufenican, flufenpyr,flufenpyr-ethyl, flumetsulam, flumezin, flumiclorac, flumiclorac-pentyl,flumioxazin, flumipropyn, fluometuron, fluorodifen, fluoroglycofen,fluoroglycofen-ethyl, fluoromidine, fluoronitrofen, fluothiuron,flupoxam, flupropacil, flupropanate, flupropanate-sodium,flupyrsulfuron, flupyrsulfuron-methyl-sodium, fluridone,flurochloridone, fluroxypyr, fluroxypyr-butometyl, fluroxypyr-meptyl,flurtamone, fluthiacet, fluthiacet-methyl, fomesafen, fomesafen-sodium,foramsulfuron, fosamine, fosamine-ammonium, furyloxyfen, glufosinate,glufosinate-ammonium, glufosinate-P, glufosinate-P-ammonium,glufosinate-P-sodium, glyphosate, glyphosate-diammonium,glyphosate-dimethylammonium, glyphosate-isopropylammonium,glyphosate-monoammonium, glyphosate-potassium, glyphosate-sesquisodium,glyphosate-trimesium, halosafen, halo sulfuron, halosulfuron-methyl,haloxydine, haloxyfop, haloxyfop-etotyl, haloxyfop-methyl, haloxyfop-P,haloxyfop-P-etotyl, haloxyfop-P-methyl, haloxyfop-sodium,hexachloroacetone, hexaflumte, hexazinone, imazamethabenz,imazamethabenz-methyl, imazamox, imazamox-ammonium, imazapic,imazapic-ammonium, imazapyr, imazapyr-isopropylammonium, imazaquin,imazaquin-ammonium, imazaquin-methyl, imazaquin-sodium, imazethapyr,imazethapyr-ammonium, imazosulfuron, indanofan, indaziflam, iodobonil,iodomethane, iodosulfuron, iodosulfuron-methyl-sodium, ioxynil, ioxyniloctanoate, ioxynil-lithium, ioxynil-sodium, ipazine, ipfencarbazone,iprymidam, isocarbamid, isocil, isomethiozin, isonoruron, isopolinate,isopropalin, isoproturon, isouron, isoxaben, isoxachlortole,isoxaflutole, isoxapyrifop, karbutilate, ketospiradox, lactofen,lenacil, linuron, MAA, MAMA, MCPA, MCPA-2-ethylhexyl, MCPA-butotyl,MCPA-butyl, MCPA-dimethylammonium, MCPA-diolamine, MCPA-ethyl,MCPA-isobutyl, MCPA-isoctyl, MCPA-isopropyl, MCPA-methyl, MCPA-olamine,MCPA-potassium, MCPA-sodium, MCPA-thioethyl, MCPA-trolamine, MCPB,MCPB-ethyl, MCPB-methyl, MCPB-sodium, mecoprop, mecoprop-2-ethylhexyl,mecoprop-dimethylammonium, mecoprop-diolamine, mecoprop-ethadyl,mecoprop-isoctyl, mecoprop-methyl, mecoprop-P,mecoprop-P-dimethylammonium, mecoprop-P-isobutyl, mecoprop-potassium,mecoprop-P-potassium, mecoprop-sodium, mecoprop-trolamine, medinoterb,medinoterb acetate, mefenacet, mefluidide, mefluidide-diolamine,mefluidide-potassium, mesoprazine, mesosulfuron, mesosulfuron-methyl,mesotrione, metam, metam-ammonium, metamifop, metamitron,metam-potassium, metam-sodium, metazachlor, metazosulfuron, metflumzon,methabenzthiazuron, methalpropalin, methazole, methiobencarb,methiozolin, methiuron, methometon, methoprotryne, methyl bromide,methyl isothiocyanate, methyldymron, metobenzuron, metolachlor,metosulam, metoxuron, metribuzin, metsulfuron, metsulfuron-methyl,molinate, monalide, monisouron, monochloroacetic acid, monolinuron,monuron, monuron TCA, morfamquat, morfamquat dichloride, MSMA,naproanilide, napropamide, naptalam, naptalam-sodium, neburon,nicosulfuron, nipyraclofen, nitmlin, nitrofen, nitrofluorfen,norflumzon, noriron, OCH, orbencarb, ortho-dichlorobenzene,orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxapyrazon,oxapyrazon-dimolamine, oxapyrazon-sodium, oxasulfuron, oxaziclomefone,oxyfluorfen, parafluron, pamquat, pamquat dichloride, pamquatdimetilsulfate, pebulate, pelargonic acid, pendimethalin, penoxsulam,pentachlorophenol, pentanochlor, pentoxazone, perfluidone, pethoxamid,phenisopham, phenmedipham, phenmedipham-ethyl, phenobenzuron,phenylmercury acetate, picloram, picloram-2-ethylhexyl,picloram-isoctyl, picloram-methyl, picloram-olamine, picloram-potassium,picloram-triethylammonium, picloram-tris(2-hydroxypropyl)ammonium,picolinafen, pinoxaden, piperophos, potassium arsenite, potassium azide,potassium cyanate, pretilachlor, primisulfuron, primisulfuron-methyl,procyazine, prodiamine, profluazol, proflumlin, profoxydim,proglinazine, proglinazine-ethyl, prometon, prometlyn, propachlor,propanil, propaquizafop, propazine, propham, propisochlor,propoxycarbazone, propoxycarbazone-sodium, propyrisulfuron, propyzamide,prosulfalin, prosulfocarb, prosulfuron, proxan, proxan-sodium,piynachlor, pydanon, pyraclonil, pyraflufen, pyraflufen-ethyl,pymsulfotole, pyrazolynate, pyrazosulfuron, pyrazosulfuron-ethyl,pyrazoxyfen, pyribenzoxim, pyributicarb, pyriclor, pyridafol, pyridate,pyriftalid, pyriminobac, pyriminobac-methyl, pyrimisulfan, pyrithiobac,pyrithiobac-sodium, pyroxasulfone, pyroxsulam, quinclorac, quinmerac,quinoclamine, quinonamid, quizalofop, quizalofop-ethyl, quizalofop-P,quizalofop-P-ethyl, quizalofop-P-tefuryl, rhodethanil, rimsulfuron,saflufenacil, sebuthylazine, secbumeton, sethoxydim, siduron, simazine,simeton, simetryn, SMA, S-metolachlor, sodium arsenite, sodium azide,sodium chlorate, sulcotrione, sulfallate, sulfentrazone, sulfometuron,sulfometuron-methyl, sulfosulfuron, sulfuric acid, sulglycapin, swep,TCA, TCA-ammonium, TCA-calcium, TCA-ethadyl, TCA-magnesium, TCA-sodium,tebutam, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim,terbacil, terbucarb, terbuchlor, terbumeton, terbuthylazine, terbutryn,tetmfluron, thenylchlor, thiazafluron, thiazopyr, thidiazimin,thidiazuron, thiencarbazone, thiencarbazone-methyl, thifensulfuron,thifensulfuron-methyl, thiobencarb, tiocarbazil, tioclorim, topramezone,tralkoxydim, tri-allate, triasulfuron, triaziflam, tribenuron,tribenuron-methyl, tricamba, triclopyr, triclopyr-butotyl,triclopyr-ethyl, triclopyr-triethylammonium, tridiphane, trietazine,trifloxysulfuron, trifloxysulfuron-sodium, trifluralin, triflusulfuron,triflusulfuron-methyl, trifop, trifop-methyl, trifopsime,trihydroxytriazine, trimeturon, tripropindan, tritac, tritosulfuron,vernolate, or xylachlor.

Biopesticides

The compound of formula I may also be used in combination (such as in acompositional mixture, or a simultaneous or sequential application) withone or more biopesticides. The term “biopesticide” is used for microbialbiological pest control agents that are applied in a similar manner tochemical pesticides. Commonly these are bacterial, but there are alsoexamples of fungal control agents, including Trichoderma spp. andAmpelomyces quisqualis (a control agent for grape powdery mildew).Bacillus subtilis are used to control plant pathogens. Weeds and rodentshave also been controlled with microbial agents. One well-knowninsecticide example is Bacillus thuringiensis, a bacterial disease ofLepidoptera, Coleoptera, and Diptera. Because it has little effect onother organisms, it is considered more environmentally friendly thansynthetic pesticides. Biological insecticides include products based on:

1. entomopathogenic fungi (e.g., Metarhizium anisopliae);

2. entomopathogenic nematodes (e.g., Steinernema feltiae); and

3. entomopathogenic viruses (e.g., Cydia pomonella granulovirus).

Other examples of entomopathogenic organisms include, but are notlimited to, baculoviruses, bacteria and other prokaryotic organisms,fungi, protozoa and Microsproridia. Biologically derived insecticidesinclude, but not limited to, rotenone, veratridine, as well as microbialtoxins; insect tolerant or resistant plant varieties; and organismsmodified by recombinant DNA technology to either produce insecticides orto convey an insect resistant property to the genetically modifiedorganism. In one embodiment, the molecules of Formula One may be usedwith one or more biopesticides in the area of seed treatments and soilamendments. The Manual of Biocontrol Agents gives a review of theavailable biological insecticide (and other biology-based control)products. Copping L. G. (ed.) (2004). The Manual of Biocontrol Agents(formerly the Biopesticide Manual) 3rd Edition. British Crop ProductionCouncil (BCPC), Farnham, Surrey UK.

Other Active Compounds

The compound of formula I may also be used in combination (such as in acompositional mixture, or a simultaneous or sequential application) withone or more of the following:

-   1.    3-(4-chloro-2,6-dimethylphenyl)-4-hydroxy-8-oxa-1-azaspiro[4,5]dec-3-en-2-one;-   2.    3-(4′-chloro-2,4-dimethyl[1,1′-biphenyl]-3-yl)-4-hydroxy-8-oxa-1-azaspiro[4,5]dec-3-en-2-one;-   3. 4-[[(6-chloro-3-pyridinyl)methyl]methylamino]-2(5H)-furanone;-   4.    4-[[(6-chloro-3-pyridinyl)methyl]cyclopropylamino]-2(5H)-furanone;-   5.    3-chloro-N2-[(1S)-1-methyl-2-(methylsulfonyl)ethyl]-N1-[2-methyl-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-1,2-benzenedicarboxamide;-   6. 2-cyano-N-ethyl-4-fluoro-3-methoxy-benenesulfonamide;-   7. 2-cyano-N-ethyl-3-methoxy-benzenesulfonamide;-   8. 2-cyano-3-difluoromethoxy-N-ethyl-4-fluoro-benzenesulfonamide;-   9. 2-cyano-3-fluoromethoxy-N-ethyl-benzenesulfonamide;-   10. 2-cyano-6-fluoro-3-methoxy-N,N-dimethyl-benzenesulfonamide;-   11. 2-cyano-N-ethyl-6-fluoro-3-methoxy-N-methyl-benzenesulfonamide;-   12. 2-cyano-3-difluoromethoxy-N,N-dimethylbenzenesulfon-amide;-   13.    3-(difluoromethyl)-N-[2-(3,3-dimethylbutyl)phenyl]-methyl-1H-pyrazole-4-carboxamide;-   14.    N-ethyl-2,2-dimethylpropionamide-2-(2,6-dichloro-α,α,α-trifluoro-p-tolyl)    hydrazone;-   15.    N-ethyl-2,2-dichloro-1-methylcyclopropane-carboxamide-2-(2,6-dichloro-α,α,α-trifluoro-p-tolyl)    hydrazone nicotine;-   16.    O-{(E-)-[2-(4-chloro-phenyl)-2-cyano-1-(2-trifluoromethylphenyl)-vinyl]}S-methyl    thiocarbonate;-   17.    (E)-N1-[(2-chloro-1,3-thiazol-5-ylmethyl)]-N2-cyano-N1-methylacetamidine;-   18.    1-(6-chloropyridin-3-ylmethyl)-7-methyl-8-nitro-1,2,3,5,6,7-hexahydro-imidazo[1,2-a]pyridin-5-ol;-   19. 4-[4-chlorophenyl-(2-butylidine-hydrazono)methyl)]phenyl    mesylate; and-   20.    N-ethyl-2,2-dichloro-1-methylcyclopropanecarboxamide-2-(2,6-dichloro-α,α,α-trifluoro-p-tolyl)hydrazone.

The compound of formula I may also be used in combination (such as in acompositional mixture, or a simultaneous or sequential application) withone or more compounds in the following groups: algicides, antifeedants,avicides, bactericides, bird repellents, chemosterilants, herbicidesafeners, insect attractants, insect repellents, mammal repellents,mating disrupters, molluscicides, plant activators, plant growthregulators, rodenticides, or virucides.

Synergistic Mixtures and Synergists

The compound of formula I may be used in combination with at least oneother insecticides to form a synergistic mixture where the mode ofaction of such compounds compared to the mode of action of the compoundof formula I are the same, similar, or different. Examples of modes ofaction may include, but are not limited to: acetylcholinesteraseinhibitor; sodium channel modulator; chitin biosynthesis inhibitor;GABA-gated chloride channel antagonist; GABA and glutamate-gatedchloride channel agonist; acetylcholine receptor agonist; MET Iinhibitor; Mg-stimulated ATPase inhibitor; nicotinic acetylcholinereceptor; Midgut membrane disrupter; oxidative phosphorylationdisrupter, or ryanodine receptor (RyRs).

Additionally, the compound of formula I may be used in combination withat least one of fungicides, acaricides, herbicides or nematicides toform a synergistic mixture.

Furthermore, the compound of formula I may be used in combination withother active compounds, such as the compounds under the heading “OTHERACTIVE COMPOUNDS,” algicides, avicides, bactericides, molluscicides,rodenticides, virucides, herbicide safeners, adjuvants, and/orsurfactants to form a synergistic mixture. Moreover, the followingcompounds are known as synergists and may be used in combination withthe compound of formula I: piperonyl butoxide, piprotal, propyl isome,sesamex, sesamolin, sulfoxide, and tribufos.

Formulations

A pesticide is rarely suitable for application in its pure form. It isusually necessary to add other substances so that the pesticide can beused at the required concentration and in an appropriate form,permitting ease of application, handling, transportation, storage, andmaximum pesticide activity. Thus, pesticides are formulated into, forexample, baits, concentrated emulsions, dusts, emulsifiableconcentrates, fumigants, gels, granules, microencapsulations, seedtreatments, suspension concentrates, suspoemulsions, tablets, watersoluble liquids, water dispersible granules or thy flowables, wettablepowders, and ultra low volume solutions. For further information onformulation types see “Catalogue of Pesticide Formulation Types andInternational Coding System” Technical Monograph n°2, 5th Edition byCropLife International (2002).

Pesticides are applied most often as aqueous suspensions or emulsionsprepared from concentrated formulations of such pesticides. Suchwater-soluble, water-suspendable, or emulsifiable formulations areeither solids, usually known as wettable powders, or water dispersiblegranules, or liquids usually known as emulsifiable concentrates, oraqueous suspensions. Wettable powders, which may be compacted to formwater dispersible granules, comprise an intimate mixture of thepesticide, a carrier, and surfactants. The concentration of thepesticide is usually from about 10% to about 90% by weight. The carrieris usually selected from among the attapulgite clays, themontmorillonite clays, the diatomaceous earths, or the purifiedsilicates. Effective surfactants, comprising from about 0.5% to about10% of the wettable powder, are found among sulfonated lignins,condensed naphthalenesulfonates, naphthalenesulfonates,alkylbenzenesulfonates, alkyl sulfates, and non-ionic surfactants suchas ethylene oxide adducts of alkyl phenols.

Emulsifiable concentrates of pesticides comprise a convenientconcentration of a pesticide, such as from about 50 to about 500 gramsper liter of liquid dissolved in a carrier that is either a watermiscible solvent or a mixture of water-immiscible organic solvent andemulsifiers. Useful organic solvents include aromatics, especiallyxylenes and petroleum fractions, especially the high-boilingnaphthalenic and olefinic portions of petroleum such as heavy aromaticnaphtha Other organic solvents may also be used, such as the terpenicsolvents including rosin derivatives, aliphatic ketones such ascyclohexanone, and complex alcohols such as 2-ethoxyethanol. Suitableemulsifiers for emulsifiable concentrates are selected from conventionalanionic and non-ionic surfactants.

Aqueous suspensions comprise suspensions of water-insoluble pesticidesdispersed in an aqueous carrier at a concentration in the range fromabout 5% to about 50% by weight. Suspensions are prepared by finelygrinding the pesticide and vigorously mixing it into a carrier comprisedof water and surfactants. Ingredients, such as inorganic salts andsynthetic or natural gums may also be added, to increase the density andviscosity of the aqueous carrier. It is often most effective to grindand mix the pesticide at the same time by preparing the aqueous mixtureand homogenizing it in an implement such as a sand mill, ball mill, orpiston-type homogenizer.

Pesticides may also be applied as granular compositions that areparticularly useful for applications to the soil. Granular compositionsusually contain from about 0.5% to about 10% by weight of the pesticide,dispersed in a carrier that comprises clay or a similar substance. Suchcompositions are usually prepared by dissolving the pesticide in asuitable solvent and applying it to a granular carrier which has beenpre-formed to the appropriate particle size, in the range of from about0.5 to about 3 mm. Such compositions may also be formulated by making adough or paste of the carrier and compound and crushing and drying toobtain the desired granular particle size.

Dusts containing a pesticide are prepared by intimately mixing thepesticide in powdered form with a suitable dusty agricultural carrier,such as kaolin clay, ground volcanic rock, and the like. Dusts cansuitably contain from about 1% to about 10% of the pesticide. They canbe applied as a seed dressing or as a foliage application with a dustblower machine.

It is equally practical to apply a pesticide in the form of a solutionin an appropriate organic solvent, usually petroleum oil, such as thespray oils, which are widely used in agricultural chemistry.

Pesticides can also be applied in the form of an aerosol composition. Insuch compositions the pesticide is dissolved or dispersed in a carrier,which is a pressure-generating propellant mixture. The aerosolcomposition is packaged in a container from which the mixture isdispensed through an atomizing valve.

Pesticide baits are formed when the pesticide is mixed with food or anattractant or both. When the pests eat the bait they also consume thepesticide. Baits may take the form of granules, gels, flowable powders,liquids, or solids. They can be used in pest harborages.

Fumigants are pesticides that have a relatively high vapor pressure andhence can exist as a gas in sufficient concentrations to kill pests insoil or enclosed spaces. The toxicity of the fumigant is proportional toits concentration and the exposure time. They are characterized by agood capacity for diffusion and act by penetrating the pest'srespiratory system or being absorbed through the pest's cuticle.Fumigants are applied to control stored product pests under gas proofsheets, in gas sealed rooms or buildings or in special chambers.

Pesticides can be microencapsulated by suspending the pesticideparticles or droplets in plastic polymers of various types. By alteringthe chemistry of the polymer or by changing factors in the processing,microcapsules can be formed of various sizes, solubility, wallthicknesses, and degrees of penetrability. These factors govern thespeed with which the active ingredient within is released, which inturn, affects the residual performance, speed of action, and odor of theproduct.

Oil solution concentrates are made by dissolving pesticide in a solventthat will hold the pesticide in solution. Oil solutions of a pesticideusually provide faster knockdown and kill of pests than otherformulations due to the solvents themselves having pesticidal action andthe dissolution of the waxy covering of the integument increasing thespeed of uptake of the pesticide. Other advantages of oil solutionsinclude better storage stability, better penetration of crevices, andbetter adhesion to greasy surfaces.

Another embodiment is an oil-in-water emulsion, wherein the emulsioncomprises oily globules which are each provided with a lamellar liquidcrystal coating and are dispersed in an aqueous phase, wherein each oilyglobule comprises at least one compound which is agriculturally active,and is individually coated with a monolamellar or oligolamellar layercomprising: (1) at least one non-ionic lipophilic surface-active agent,(2) at least one non-ionic hydrophilic surface-active agent and (3) atleast one ionic surface-active agent, wherein the globules having a meanparticle diameter of less than 800 nanometers. Further information onthe embodiment is disclosed in U.S. patent publication 20070027034published Feb. 1, 2007, having patent application Ser. No. 11/495,228.For ease of use, this embodiment will be referred to as “OIWE”.

For further information consult “Insect Pest Management” 2nd Edition byD. Dent, copyright CAB International (2000). Additionally, for moredetailed information consult “Handbook of Pest Control—The Behavior,Life History, and Control of Household Pests” by Arnold Mallis, 9thEdition, copyright 2004 by GIE Media Inc.

Other Formulation Components

Generally, when compound of formula I and/or any agriculturallyacceptable salt thereof, are used in a formulation, such formulation canalso contain other components. These components include, but are notlimited to, (this is a non-exhaustive and non-mutually exclusive list)welters, spreaders, stickers, penetrants, buffers, sequestering agents,drift reduction agents, compatibility agents, anti-foam agents, cleaningagents, and emulsifiers. A few components are described forthwith.

A wetting agent is a substance that when added to a liquid increases thespreading or penetration power of the liquid by reducing the interfacialtension between the liquid and the surface on which it is spreading.Wetting agents are used for two main functions in agrochemicalformulations: during processing and manufacture to increase the rate ofwetting of powders in water to make concentrates for soluble liquids orsuspension concentrates; and during mixing of a product with water in aspray tank to reduce the wetting time of wettable powders and to improvethe penetration of water into water-dispersible granules. Examples ofwetting agents used in wettable powder, suspension concentrate, andwater-dispersible granule formulations are: sodium lauryl sulfate;sodium dioctyl sulfosuccinate; alkyl phenol ethoxylates; and aliphaticalcohol ethoxylates.

A dispersing agent is a substance which adsorbs onto the surface ofparticles and helps to preserve the state of dispersion of the particlesand prevents them from reaggregating. Dispersing agents are added toagrochemical formulations to facilitate dispersion and suspension duringmanufacture, and to ensure the particles redisperse into water in aspray tank They are widely used in wettable powders, suspensionconcentrates and water-dispersible granules. Surfactants that are usedas dispersing agents have the ability to adsorb strongly onto a particlesurface and provide a charged or steric barrier to reaggregation ofparticles. The most commonly used surfactants are anionic, non-ionic, ormixtures of the two types. For wettable powder formulations, the mostcommon dispersing agents are sodium lignosulfonates. For suspensionconcentrates, very good adsorption and stabilization are obtained usingpolyelectrolytes, such as sodium naphthalene sulfonate formaldehydecondensates. Tristyrylphenol ethoxylate phosphate esters are also used.Non-ionics such as alkylaiylethylene oxide condensates and EO-PO blockcopolymers are sometimes combined with anionics as dispersing agents forsuspension concentrates. In recent years, new types of very highmolecular weight polymeric surfactants have been developed as dispersingagents. These have very long hydrophobic ‘backbones’ and a large numberof ethylene oxide chains forming the ‘teeth’ of a ‘comb’ surfactant.These high molecular weight polymers can give very good long-termstability to suspension concentrates because the hydrophobic backboneshave many anchoring points onto the particle surfaces. Examples ofdispersing agents used in agrochemical formulations are: sodiumlignosulfonates; sodium naphthalene sulfonate formaldehyde condensates;tristyrylphenol ethoxylate phosphate esters; aliphatic alcoholethoxylates; alkyl ethoxylates; EO-PO block copolymers; and graftcopolymers.

An emulsifying agent is a substance which stabilizes a suspension ofdroplets of one liquid phase in another liquid phase. Without theemulsifying agent the two liquids would separate into two immiscibleliquid phases. The most commonly used emulsifier blends containalkylphenol or aliphatic alcohol with twelve or more ethylene oxideunits and the oil-soluble calcium salt of dodecylbenzenesulfonic acid. Arange of hydrophile-lipophile balance (“HLB”) values from 8 to 18 willnormally provide good stable emulsions. Emulsion stability can sometimesbe improved by the addition of a small amount of an EO-PO blockcopolymer surfactant.

A solubilizing agent is a surfactant which will form micelles in waterat concentrations above the critical micelle concentration. The micellesare then able to dissolve or solubilize water-insoluble materials insidethe hydrophobic part of the micelle. The types of surfactants usuallyused for solubilization are non-ionics, sorbitan monooleates, sorbitanmonooleate ethoxylates, and methyl oleate esters.

Surfactants are sometimes used, either alone or with other additivessuch as mineral or vegetable oils as adjuvants to spray-tank mixes toimprove the biological performance of the pesticide on the target. Thetypes of surfactants used for bioenhancement depend generally on thenature and mode of action of the pesticide. However, they are oftennon-ionics such as: alkyl ethoxylates; linear aliphatic alcoholethoxylates; aliphatic amine ethoxylates.

A carrier or diluent in an agricultural formulation is a material addedto the pesticide to give a product of the required strength. Carriersare usually materials with high absorptive capacities, while diluentsare usually materials with low absorptive capacities. Carriers anddiluents are used in the formulation of dusts, wettable powders,granules and water-dispersible granules.

Organic solvents are used mainly in the formulation of emulsifiableconcentrates, oil-in-water emulsions, suspoemulsions, and ultra lowvolume formulations, and to a lesser extent, granular formulations.Sometimes mixtures of solvents are used. The first main groups ofsolvents are aliphatic paraffinic oils such as kerosene or refinedparaffins. The second main group (and the most common) comprises thearomatic solvents such as xylene and higher molecular weight fractionsof C9 and C10 aromatic solvents. Chlorinated hydrocarbons are useful ascosolvents to prevent crystallization of pesticides when the formulationis emulsified into water. Alcohols are sometimes used as cosolvents toincrease solvent power. Other solvents may include vegetable oils, seedoils, and esters of vegetable and seed oils.

Thickeners or gelling agents are used mainly in the formulation ofsuspension concentrates, emulsions and suspoemulsions to modify therheology or flow properties of the liquid and to prevent separation andsettling of the dispersed particles or droplets. Thickening, gelling,and anti-settling agents generally fall into two categories, namelywater-insoluble particulates and water-soluble polymers. It is possibleto produce suspension concentrate formulations using clays and silicas.Examples of these types of materials, include, but are not limited to,montmorillonite, bentonite, magnesium aluminum silicate, andattapulgite. Water-soluble polysaccharides have been used asthickening-gelling agents for many years. The types of polysaccharidesmost commonly used are natural extracts of seeds and seaweeds or aresynthetic derivatives of cellulose. Examples of these types of materialsinclude, but are not limited to, guar gum; locust bean gum; carrageenam;alginates; methyl cellulose; sodium carboxymethyl cellulose (SCMC);hydroxyethyl cellulose (HEC). Other types of anti-settling agents arebased on modified starches, polyacrylates, polyvinyl alcohol andpolyethylene oxide. Another good anti-settling agent is xanthan gum.

Microorganisms can cause spoilage of formulated products. Therefore,preservation agents are used to eliminate or reduce their effect.Examples of such agents include, but are not limited to: propionic acidand its sodium salt; sorbic acid and its sodium or potassium salts;benzoic acid and its sodium salt; p-hydroxybenzoic acid sodium salt;methyl p-hydroxybenzoate; and 1,2-benzisothiazolin-3-one (BIT).

The presence of surfactants often causes water-based formulations tofoam during mixing operations in production and in application through aspray tank. In order to reduce the tendency to foam, anti-foam agentsare often added either during the production stage or before fillinginto bottles. Generally, there are two types of anti-foam agents, namelysilicones and non-silicones. Silicones are usually aqueous emulsions ofdimethyl polysiloxane, while the non-silicone anti-foam agents arewater-insoluble oils, such as octanol and nonanol, or silica. In bothcases, the function of the anti-foam agent is to displace the surfactantfrom the air-water interface.

“Green” agents (e.g., adjuvants, surfactants, solvents) can reduce theoverall environmental footprint of crop protection formulations. Greenagents are biodegradable and generally derived from natural and/orsustainable sources, e.g., plant and animal sources. Specific examplesare: vegetable oils, seed oils, and esters thereof, also alkoxylatedalkyl polyglucosides.

For further information, see “Chemistry and Technology of AgrochemicalFormulations” edited by D. A. Knowles, copyright 1998 by Kluwer AcademicPublishers. Also see “Insecticides in Agriculture andEnvironment—Retrospects and Prospects” by A. S. Perry, I. Yamamoto, I.Ishaaya, and R. Perry, copyright 1998 by Springer-Verlag.

Pesticidal Activities

The disclosed pesticidal compositions may be used, for example, asnematicides, acaricides, pesticides, insecticides, miticides, and/ormolluscicides.

In one particular embodiment, a method of controlling pests comprisesapplying a pesticidal composition comprising at least one compoundsselected from a compound of formula I, or any agriculturally acceptablesalt thereof, near a population of pests.

The compound of formula I are generally used in amounts from about 0.01grams per hectare to about 5000 grams per hectare to provide control.Amounts from about 0.1 grams per hectare to about 500 grams per hectareare generally preferred, and amounts from about 1 gram per hectare toabout 50 grams per hectare are generally more preferred.

The area to which a compound of formula I is applied can be any areainhabited (or maybe inhabited, or traversed by) a pest, for example:where crops, trees, fruits, cereals, fodder species, vines, turf andornamental plants, are growing; where domesticated animals are residing;the interior or exterior surfaces of buildings (such as places wheregrains are stored), the materials of construction used in building (suchas impregnated wood), and the soil around buildings. Particular cropareas to use a molecule of Formula One include areas where apples, corn,sunflowers, cotton, soybeans, canola, wheat, rice, sorghum, barley,oats, potatoes, oranges, alfalfa, lettuce, strawberries, tomatoes,peppers, crucifers, pears, tobacco, almonds, sugar beets, beans andother valuable crops are growing or the seeds thereof are going to beplanted. It is also advantageous to use ammonium sulfate with acompounds of formula I when growing various plants.

Controlling pests generally means that pest populations, pest activity,or both, are reduced in an area. This can come about when: pestpopulations are repulsed from an area; when pests are incapacitated inor around an area; or pests are exterminated, in whole, or in part, inor around an area. Of course, a combination of these results can occur.Generally, pest populations, activity, or both are desirably reducedmore than fifty percent, preferably more than 90 percent. Generally, thearea is not in or on a human; consequently, the locus is generally anon-human area.

The compound of formula I may be used in mixtures, appliedsimultaneously or sequentially, alone or with other compounds to enhanceplant vigor (e.g., to grow a better root system, to better withstandstressful growing conditions). Such other compounds are, for example,compounds that modulate plant ethylene receptors, most notably1-methylcyclopropene (also known as 1-MCP). Furthermore, such moleculesmay be used during times when pest activity is low, such as before theplants that are growing begin to produce valuable agriculturalcommodities. Such times include the early planting season when pestpressure is usually low.

The compound of formula I can be applied to the foliar and fruitingportions of plants to control pests. The molecules will either come indirect contact with the pest, or the pest will consume the pesticidewhen eating leaf, fruit mass, or extracting sap, that contains thepesticide. The compound of formula I can also be applied to the soil,and when applied in this manner, root and stem feeding pests can becontrolled. The roots can absorb a molecule taking it up into the foliarportions of the plant to control above ground chewing and sap feedingpests.

Generally, with baits, the baits are placed in the ground where, forexample, termites can come into contact with, and/or be attracted to,the bait. Baits can also be applied to a surface of a building,(horizontal, vertical, or slant surface) where, for example, ants,termites, cockroaches, and flies, can come into contact with, and/or beattracted to, the bait. Baits can comprise a compounds of formula I.

The compound of formula I can be encapsulated inside, or placed on thesurface of a capsule. The size of the capsules can range from nanometersize (about 100-900 nanometers in diameter) to micrometer size (about10-900 microns in diameter).

Because of the unique ability of the eggs of some pests to resistcertain pesticides, repeated applications of the compound of formula Imay be desirable to control newly emerged larvae.

Systemic movement of pesticides in plants may be utilized to controlpests on one portion of the plant by applying (for example, by sprayingan area) the compounds of formula I to a different portion of the plant.For example, control of foliar-feeding insects can be achieved by dripirrigation or furrow application, by treating the soil with, forexample, pre- or post-planting soil drench, or by treating the seeds ofa plant before planting.

Seed treatment can be applied to all types of seeds, including thosefrom which plants genetically modified to express specialized traitswill germinate. Representative examples include those expressingproteins toxic to invertebrate pests, such as Bacillus thuringiensis orother insecticidal toxins, those expressing herbicide resistance, suchas “Roundup Ready” seed, or those with “stacked” foreign genesexpressing insecticidal toxins, herbicide resistance,nutrition-enhancement, drought resistance, or any other beneficialtraits. Furthermore, such seed treatments with the compounds of formulaI may further enhance the ability of a plant to better withstandstressful growing conditions. This results in a healthier, more vigorousplant, which can lead to higher yields at harvest time. Generally, about1 gram of the compound of formula I to about 500 grams per 100,000 seedsis expected to provide good benefits, amounts from about 10 grams toabout 100 grams per 100,000 seeds is expected to provide betterbenefits, and amounts from about 25 grams to about 75 grams per 100,000seeds is expected to provide even better benefits.

It should be readily apparent that the compound of formula I may be usedon, in, or around plants genetically modified to express specializedtraits, such as Bacillus thuringiensis or other insecticidal toxins, orthose expressing herbicide resistance, or those with “stacked” foreigngenes expressing insecticidal toxins, herbicide resistance,nutrition-enhancement, or any other beneficial traits.

The compound of formula I may be used for controlling endoparasites andectoparasites in the veterinary medicine sector or in the field ofnon-human animal keeping. The compound of formula I may be applied, suchas by oral administration in the form of, for example, tablets,capsules, drinks, granules, by dermal application in the form of, forexample, dipping, spraying, pouring on, spotting on, and dusting, and byparenteral administration in the form of, for example, an injection.

The compound of formula I may also be employed advantageously inlivestock keeping, for example, cattle, sheep, pigs, chickens, andgeese. They may also be employed advantageously in pets such as, horses,dogs, and cats. Particular pests to control would be fleas and ticksthat are bothersome to such animals. Suitable formulations areadministered orally to the animals with the drinking water or feed. Thedosages and formulations that are suitable depend on the species.

The compound of formula I may also be used for controlling parasiticworms, especially of the intestine, in the animals listed above.

The compound of formula I may also be employed in therapeutic methodsfor human health care. Such methods include, but are limited to, oraladministration in the form of, for example, tablets, capsules, drinks,granules, and by dermal application.

Pests around the world have been migrating to new environments (for suchpest) and thereafter becoming a new invasive species in such newenvironment. The compounds of formula I may also be used on such newinvasive species to control them in such new environment.

The compound of formula I may also be used in an area where plants, suchas crops, are growing (e.g., pre-planting, planting, pre-harvesting) andwhere there are low levels (even no actual presence) of pests that cancommercially damage such plants. The use of such molecules in such areais to benefit the plants being grown in the area. Such benefits, mayinclude, but are not limited to, improving the health of a plant,improving the yield of a plant (e.g., increased biomass and/or increasedcontent of valuable ingredients), improving the vigor of a plant (e.g.,improved plant growth and/or greener leaves), improving the quality of aplant (e.g., improved content or composition of certain ingredients),and improving the tolerance to abiotic and/or biotic stress of theplant.

Before a pesticide can be used or sold commercially, such pesticideundergoes lengthy evaluation processes by various governmentalauthorities (local, regional, state, national, and international).Voluminous data requirements are specified by regulatory authorities andmust be addressed through data generation and submission by the productregistrant or by a third party on the product registrant's behalf, oftenusing a computer with a connection to the World Wide Web. Thesegovernmental authorities then review such data and if a determination ofsafety is concluded, provide the potential user or seller with productregistration approval. Thereafter, in that locality where the productregistration is granted and supported, such user or seller may use orsell such pesticide.

A compound of formula I can be tested to determine its efficacy againstpests. Furthermore, mode of action studies can be conducted to determineif said molecule has a different mode of action than other pesticides.Thereafter, such acquired data can be disseminated, such as by theinternet, to third parties.

The disclosed pesticidal composition comprising compound of formula Imay be used to control a wide variety of pests.

As a non-limiting example, in one or more embodiments, the method of thepresent disclosure may be used to control one or more members ofLyriomiza sativae, Caliothrips phaseoli, Parafrioza cockerel, Spodopteraexigua, Myzus persicae, Nilaparvata lugens, Bemisia tabaci.

In additional embodiments, the method of the present disclosure may beused to control one or more members of at least one of PhylumArthropoda, Phylum Nematoda, Subphylum Chelicemta, Subphylum Myriapoda,Subphylum Hexapoda, Class Insecta, Class Arachnida, and Class Symphyla.In at least some embodiments, the method of the present disclosure maybe used to control one or more members of at least one of Class Insectaand Class Arachnida.

In further embodiments, the method of the present disclosure may be usedto control members of the Order Coleoptera (beetles) including, but notlimited to, Acanthoscelides spp. (weevils), Acanthoscelides obtectus(common bean weevil), Agrilus planipennis (emerald ash borer), Agriotesspp. (wireworms), Anoplophora glabripennis (Asian longhorned beetle),Anthonomus spp. (weevils), Anthonomus grandis (boll weevil), Aphidiusspp., Apion spp. (weevils), Apogonia spp. (grubs), Ataenius spretulus(Black Turfgrass Ataenius), Atomaria linearis (pygmy mangold beetle),Aulacophore spp., Bothynoderes punctivenfris (beet root weevil), Bruchusspp. (weevils), Bruchus pisorum (pea weevil), Cacoesia spp.,Callosobruchus maculates (southern cow pea weevil), Carpophilushemipteras (dried fruit beetle), Cassida vittata, Cerosterna spp.,Cerotoma spp. (chiysomelids), Cerotoma trifurcata (bean leaf beetle),Ceutorhynchus spp. (weevils), Ceutorhynchus assimilis (cabbage seedpodweevil), Ceutorhynchus napi (cabbage curculio), Chaetocnema spp.(chiysomelids), Colaspis spp. (soil beetles), Conoderus scalaris,Conoderus stigmosus, Conotrachelus nenuphar (plum curculio), Cotinusnitidis (Green June beetle), Crioceris asparagi (asparagus beetle),Cryptolestes ferrugineus (rusty grain beetle), Cryptolestes pusillus(flat grain beetle), Cryptolestes turcicus (Turkish grain beetle),Ctenicera spp. (wireworms), Curculio spp. (weevils), Cyclocephala spp.(grubs), Cylindrocpturus adspersus (sunflower stem weevil), Deporausmarginatus (mango leaf-cutting weevil), Dermestes lardarius (larderbeetle), Dermestes maculates (hide beetle), Diabrotica spp.(chiysomelids), Epilachna varivestis (Mexican bean beetle), Faustinuscubae, Hylobius pales (pales weevil), Hypera spp. (weevils), Hyperapostica (alfalfa weevil), Hyperdoes spp. (Hyperodes weevil),Hypothenemus hampei (coffee berry beetle), Ips spp. (engravers),Lasioderma serricome (cigarette beetle), Leptinotarsa decemlineata(Colorado potato beetle), Liogenys fuscus, Liogenys suturalis,Lissorhopfrus oryzophilus (rice water weevil), Lyctus spp. (woodbeetles/powder post beetles), Maecolaspis joliveti, Megascelis spp.,Melanotus communis, Meligethes spp., Meligethes aeneus (blossom beetle),Melolontha melolontha (common European cockchafer), Oberea brevis,Oberea linearis, Oryctes rhinoceros (date palm beetle), Oryzaephilusmercator (merchant grain beetle), Oryzaephilus surinamensis (sawtoothedgrain beetle), Otiorhynchus spp. (weevils), Oulema melanopus (cerealleaf beetle), Oulema oryzae, Pantomorus spp. (weevils), Phyllophaga spp.(May/June beetle), Phyllophaga cuyabana (chiysomelids), Phynchites spp.,Popillia japonica (Japanese beetle), Prostephanus truncates (largergrain borer), Rhizopertha dominica (lesser grain borer), Rhizotrogusspp. (European chafer), Rhynchophorus spp. (weevils), Scolytus spp.(wood beetles), Shenophorus spp. (Billbug), Sitona lineatus (pea leafweevil), Sitophilus spp. (grain weevils), Sitophilus granaries (granaryweevil), Sitophilus oryzae (rice weevil), Stegobium paniceum (drugstorebeetle), Tribolium spp. (flour beetles), Tribolium castaneum (red flourbeetle), Tribolium confusum (confused flour beetle), Trogodermavariabile (warehouse beetle), and Zabrus tenebioides.

In other embodiments, the method of the present disclosure may also beused to control members of the Order Dermaptera (earwigs).

In additional embodiments, the method of the present disclosure may beused to control members of the Order Dictyoptera (cockroaches)including, but is not limited to, Blattella germanica (Germancockroach), Blatta orientalis (oriental cockroach), Parcoblattapennylvanica, Periplaneta americana (American cockroach), Periplanetaausfraloasiae (Australian cockroach), Periplaneta brunnea (browncockroach), Periplaneta fuliginosa (smokybrown cockroach), Pyncoselussuninamensis (Surinam cockroach), and Supella longipalpa (brownbandedcockroach).

In further embodiments, the method of the present disclosure may be usedto control members of the Order Diptera (true flies) including, but isnot limited to, Aedes spp. (mosquitoes), Agromyza frontella (alfalfablotch leafminer), Agromyza spp. (leaf miner flies), Anastrepha spp.(fruit flies), Anasfrepha suspensa (Caribbean fruit fly), Anopheles spp.(mosquitoes), Batrocera spp. (fruit flies), Bacfrocera cucurbitae (melonfly), Bactrocera dorsalis (oriental fruit fly), Ceratitis spp. (fruitflies), Ceratitis capitata (Mediterranean fruit fly), Chrysops spp.(deer flies), Cochliomyia spp. (screwworms), Contarinia spp. (Gallmidges), Culex spp. (mosquitoes), Dasineura spp. (gall midges),Dasineura brassicae (cabbage gall midge), Delia spp., Delia platura(seedcorn maggot), Drosophila spp. (vinegar flies), Fannia spp. (filthflies), Fannia canicularis (little house fly), Fannia scalaris (latrinefly), Gasterophilus intestinalis (horse bot fly), Gracillia perseae,Haematobia irritans (horn fly), Hylemyia spp. (root maggots), Hypodermalineatum (common cattle grub), Liriomyza spp. (leafminer flies),Liriomyza brassica (serpentine leafminer), Melophagus ovinus (sheepked), Musca spp. (muscid flies), Musca autumnalis (face fly), Muscadomestica (house fly), Oestrus ovis (sheep bot fly), Oscinella frit(frit fly), Pegomyia betae (beet leafminer), Phorbia spp., Psila rosae(carrot rust fly), Rhagoletis cerasi (cherry fruit fly), Rhagoletispomonella (apple maggot), Sitodiplosis mosellana (orange wheat blossommidge), Stomoxys calcitrans (stable fly), Tabanus spp. (horse flies),and Tipula spp. (crane flies).

In other embodiments, the method of the present disclosure may be usedto control members of the Order Hemiptera (true bugs) including, but isnot limited to, Acrosternum hilare (green stink bug), Blissusleucopterus (chinch bug), Calocoris norvegicus (potato mind), Cimexhemipterus (tropical bed bug), Cimex lectularius (bed bug), Dagbertusfasciatus, Dichelops furcatus, Dysdercus suturellus (cotton stainer),Edessa meditabunda, Eurygaster maura (cereal bug), Euschistus heros,Euschistus servus (brown stink bug), Helopeltis antonii, Helopeltistheivora (tea blight plantbug), Lagynotomus spp. (stink bugs),Leptocorisa oratorius, Leptocorisa varicomis, Lygus spp. (plant bugs),Lygus hesperus (western tarnished plant bug), Maconellicoccus hirsutus,Neurocolpus longirostris, Nezara viridula (southern green stink bug),Phytocoris spp. (plant bugs), Phytocoris californicus, Phytocorisrelativus, Piezodorus guildingi, Poecilocapsus lineatus (fourlined plantbug), Psallus vaccinicola, Pseudacysta perseae, Scaptocoris castanea,and Triatoma spp. (bloodsucking conenose bugs/kissing bugs).

In additional embodiments, the method of the present disclosure may beused to control members of the Order Homoptera (aphids, scales,whiteflies, leaflhoppers) including, but is not limited to,Acrythosiphon pisum (pea aphid), Adelges spp. (adelgids), Aleurodesproletella (cabbage whitefly), Aleurodicus disperses, Aleurothrixusfloccosus (woolly whitefly), Aluacaspis spp., Amrasca bigutellabigutella, Aphrophora spp. (leafhoppers), Aonidiella aurantii(California red scale), Aphis spp. (aphids), Aphis gossypii (cottonaphid), Aphis pomi (apple aphid), Aulacorthum solani (foxglove aphid),Bemisia spp. (whiteflies), Bemisia argentifolii, Bemisia tabaci(sweetpotato whitefly), Brachycolus noxius (Russian aphid),Brachycorynella asparagi (asparagus aphid), Brevennia rehi, Brevicognebrassicae (cabbage aphid), Ceroplastes spp. (scales), Ceroplastes rubens(red wax scale), Chionaspis spp. (scales), Chrysomphalus spp. (scales),Coccus spp. (scales), Dysaphis plantaginea (rosy apple aphid), Empoascaspp. (leafhoppers), Eriosoma lanigerum (woolly apple aphid), Iceryapurchasi (cottony cushion scale), Idioscopus nitidulus (mangoleafhopper), Laodelphax sfriatellus (smaller brown planthopper),Lepidosaphes spp., Macrosiphum spp., Macrosiphum euphorbiae (potatoaphid), Macrosiphum granarium (English grain aphid), Macrosiphum rosae(rose aphid), Macrosteles quadrilineatus (aster leafhopper), Mahanarvafrimbiolata, Metopolophium dirhodum (rose grain aphid), Mictislongicornis, Myzus spp., Myzus persicae (green peach aphid), Nephotettixspp. (leafhoppers), Nephotettix cinctipes (green leafhopper),Nilaparvata lugens (brown planthopper), Parlatoria pergandii (chaffscale), Parlatoria ziziphi (ebony scale), Peregrinus maidis (corndelphacid), Philaenus spp. (spittlebugs), Phylloxera vitifoliae (grapephylloxera), Physokermes piceae (spruce bud scale), Planococcus spp.(mealybugs), Pseudococcus spp. (mealybugs), Pseudococcus brevipes (pineapple mealybug), Quadraspidiotus perniciosus (San Jose scale),Rhapalosiphum spp. (aphids), Rhapalosiphum maida (corn leaf aphid),Rhapalosiphum padi (oat bird-cherry aphid), Saissetia spp. (scales),Saissetia oleae (black scale), Schizaphis graminum (greenbug), Sitobionavenae (English grain aphid), Sogatella furcifera (white-backedplanthopper), Therioaphis spp. (aphids), Toumeyella spp. (scales),Toxoptera spp. (aphids), Trialeurodes spp. (whiteflies), Trialeurodesvaporariorum (greenhouse whitefly), Trialeurodes abutiloneus (bandedwingwhitefly), Unaspis spp. (scales), Unaspis yanonensis (arrowhead scale),and Zulia enfreriana. In at least some embodiments, the method of thepresent disclosure may be used to control Myzus persicae.

In other embodiments, the method of the present disclosure may be usedto control members of the Order Hymenoptera (ants, wasps, and bees)including, but not limited to, Acromyrrmex spp., Athalia rosae, Attaspp. (leafcutting ants), Camponotus spp. (carpenter ants), Diprion spp.(sawflies), Formica spp. (ants), Iridomyrmex humilis (Argentine ant),Monomorium ssp., Monomorium minumum (little black ant), Monomoriumpharaonis (Pharaoh ant), Neodiprion spp. (sawflies), Pogonomyrmex spp.(harvester ants), Polistes spp. (paper wasps), Solenopsis spp. (fireants), Tapoinoma sessile (odorous house ant), Tefanomorium spp.(pavement ants), Vespula spp. (yellow jackets), and Xylocopa spp.(carpenter bees).

In certain embodiments, the method of the present disclosure may be usedto control members of the Order Isoptera (termites) including, but notlimited to, Coptotermes spp., Coptotermes curvignathus, Coptotermesfrenchii, Coptotermes formosanus (Formosan subterranean termite),Cornitermes spp. (nasute termites), Cryptotermes spp. (drywoodtermites), Heterotermes spp. (desert subterranean termites),Heterotermes aureus, Kalotermes spp. (drywood termites), Incistitermesspp. (drywood termites), Macrotermes spp. (fungus growing termites),Marginitermes spp. (drywood termites), Microcerotermes spp. (harvestertermites), Microtermes obesi, Procornitermes spp., Reticulitermes spp.(subterranean termites), Reticulitermes banyulensis, Reticulitermesgrassei, Reticulitermes flavipes (eastern subterranean termite),Reticulitermes hageni, Reticulitermes hesperus (western subterraneantermite), Reticulitermes santonensis, Reticulitermes speratus,Reticulitermes tibialis, Reticulitermes virginicus, Schedorhinotermesspp., and Zootermopsis spp. (rotten-wood termites).

In additional embodiments, the method of the present disclosure may beused to control members of the Order Lepidoptera (moths and butterflies)including, but not limited to, Achoea janata, Adoxophyes spp.,Adoxophyes orana, Agrotis spp. (cutworms), Agrotis ipsilon (blackcutworm), Alabama argillacea (cotton leafworm), Amorbia cuneana,Amyelosis fransitella (navel orangeworm), Anacamptodes defectaria,Anarsia lineatella (peach twig borer), Anomis sabulifera (jute looper),Anticarsia gemmatalis (velvetbean caterpillar), Archips argyrospila(fruittree leafroller), Archips rosana (rose leaf roller), Argyrotaeniaspp. (tortricid moths), Argyrotaenia citrana (orange tortrix),Autographa gamma, Bonagota cranaodes, Borbo cinnara (rice leaf folder),Bucculatrix thurberiella (cotton leafperforator), Caloptilia spp. (leafminers), Capua reticulana, Carposina niponensis (peach fruit moth),Chilo spp., Chlumetia transversa (mango shoot borer), Choristoneurarosaceana (obliquebanded leafroller), Chrysodeixis spp., Cnaphalocerusmedinalis (grass leafroller), Colias spp., Conpomorpha cramerella,Cossus cossus (carpenter moth), Crambus spp. (Sod webworms),Cydiafunebrana (plum fruit moth), Cydia molesta (oriental fruit moth),Cydia nignicana (pea moth), Cydia pomonella (codling moth), Darnadiducta, Diaphania spp. (stem borers), Diatraea spp (stalk borers),Diatraea saccharalis (sugarcane borer), Diatraea graniosella(southwester corn borer), Earias spp. (bollworms), Earias insulata(Egyptian bollworm), Earias vitella (rough northern bollworm),Ecdytopopha aurantianum, Elasmopalpus lignosellus (lesser cornstalkborer), Epiphysias postruttana (light brown apple moth), Ephestia spp.(flour moths), Ephestia cautella (almond moth), Ephestia elutella(tobbaco moth), Ephestia kuehniella (Mediterranean flour moth), Epimecesspp., Epinotia aporema, Erionota thrax (banana skipper), Eupoeciliaambiguella (grape berry moth), Euxoa auxiliaris (army cutworm), Feltiaspp. (cutworms), Gortyna spp. (stemborers), Grapholita molesta (orientalfruit moth), Hedylepta indicata (bean leaf webber), Helicoverpa spp.(noctuid moths), Helicoverpa armigera (cotton bollworm), Helicoverpa zea(bollworm/corn earworm), Heliothis spp. (noctuid moths), Heliothisvirescens (tobacco budworm), Hellula undalis (cabbage webworm),Indarbela spp. (root borers), Keiferia lycopersicella (tomato pinworm),Leucinodes orbonalis (eggplant fruit borer), Leucoptera malifoliella,Lithocollectis spp., Lobesia botrana (grape fruit moth), Loxagrotis spp.(noctuid moths), Loxagrotis albicosta (western bean cutworm), Lymantriadispar (gypsy moth), Lyonetia clerkella (apple leaf miner), Mahasenacorbetti (oil palm bagworm), Malacosoma spp. (tent caterpillars),Mamesira brassicae (cabbage armyworm), Maruca testulalis (bean podborer), Metisa plana (bagworm), Mythimna unipuncta (true armyworm),Neoleucinodes elegantalis (small tomato borer), Nymphula depunctalis(rice caseworm), Operophthera brumata (winter moth), Ostrinia nubilalis(European corn borer), Oxydia vesulia, Pandemis cerasana (common curranttortrix), Pandemis heparana (brown apple tortrix), Papilio demodocus,Pectinophora gossypiella (pink bollworm), Peridroma spp. (cutworms),Peridroma saucia (variegated cutworm), Perileucoptera coffeella (whitecoffee leafminer), Phthorimaea operculella (potato tuber moth),Phyllocnisitis citrella, Phyllonorycter spp. (leafminers), Pieris rapae(imported cabbageworm), Plathypena scabra, Plodia interpunctella (Indianmeal moth), Plutella xylostella (diamondback moth), Polychrosis viteana(grape berry moth), Prays endocarpa, Prays oleae (olive moth),Pseudaletia spp. (noctuid moths), Pseudaletia unipunctata (armyworm),Pseudoplusia includens (soybean looper), Rachiplusia nu, Scirpophagaincertulas, Sesamia spp. (stemborers), Sesamia inferens (pink rice stemborer), Sesamia nonagrioides, Setora nitens, Sitotroga cerealella(Angoumois grain moth), Sparganothis pilleriana, Spodoptera spp.(armyworms), Spodoptera exigua (beet armyworm), Spodoptera fugiperda(fall armyworm), Spodoptera oridania (southern armyworm), Synanthedonspp. (root borers), Thecla basilides, Thermisia gemmatalis, Tineolabisselliella (webbing clothes moth), Trichoplusia ni (cabbage looper),Tuta absoluta, Yponomeuta spp., Zeuzera coffeae (red branch borer), andZeuzera pyrina (leopard moth). In at least some embodiments, the methodof the present disclosure may be used to control Spodoptera exigua.

The method of the present disclosure may be used to also control membersof the Order Mallophaga (chewing lice) including, but not limited to,Bovicola ovis (sheep biting louse), Menacanthus stramineus (chicken bodylouse), and Menopon gallinea (common hen louse).

In additional embodiments, the method of the present disclosure may beused to control members of the Order Orthoptera (grasshoppers, locusts,and crickets) including, but not limited to, Anabrus simplex (Mormoncricket), Gryllotalpidae (mole crickets), Locusta migratoria, Melanoplusspp. (grasshoppers), Microcentrum retinerve (angularwinged katydid),Pterophylla spp. (kaydids), chistocerca gregaria, Scudderia furcata(forktailed bush katydid), and Valanga nigricorni.

In other embodiments, the method of the present disclosure may be usedto control members of the Order Phthiraptera (sucking lice) including,but not limited to, Haematopinus spp. (cattle and hog lice), Linognathusovillus (sheep louse), Pediculus humanus capitis (human body louse),Pediculus humanus humanus (human body lice), and Pthirus pubis (crablouse).

In particular embodiments, the method of the present disclosure may beused to control members of the Order Siphonaptera (fleas) including, butnot limited to, Ctenocephalides canis (dog flea), Ctenocephalides felis(cat flea), and Pulex irritans (human flea).

In additional embodiments, the method of the present disclosure may beused to control members of the Order Thysanoptera (thrips) including,but not limited to, Frankliniella fusca (tobacco thrips), Frankliniellaoccidentalis (western flower thrips), Frankliniella shultzei,Frankliniella williamsi (corn thrips), Heliothnps haemorrhaidalis(greenhouse thrips), Riphiphorothrips cruentatus, Scirtothrips spp.,Scirtothrips citri (citrus thrips), Scirtothrips dorsalis (yellow teathrips), Taeniothrips rhopalantennalis, and Thrips spp.

The method of the present disclosure may be used to also control membersof the Order Thysanura (bristletails) including, but not limited to,Lepisma spp. (silverfish) and Thermobia spp. (firebrats).

In further embodiments, the method of the present disclosure may be usedto control members of the Order Acari (mites and ticks) including, butnot limited to, Acarapsis woodi (tracheal mite of honeybees), Acarusspp. (food mites), Acarus siro (grain mite), Aceria mangiferae (mangobud mite), Aculops spp., Aculops lycopersici (tomato russet mite),Aculops pelekasi, Aculus pelekassi, Aculus schlechtendali (apple rustmite), Amblyomma americanum (lone star tick), Boophilus spp. (ticks),Brevipalpus obovatus (privet mite), Brevipalpus phoenicis (red and blackflat mite), Demodex spp. (mange mites), Dermacentor spp. (hard ticks),Dermacentor variabilis (american dog tick), Dermatophagoidespteronyssinus (house dust mite), Eotetranycus spp., Eotetranychuscarpini (yellow spider mite), Epitimerus spp., Eriophyes spp., Ixodesspp. (ticks), Metatetranycus spp., Notoedres cati, Oligonychus spp.,Oligonychus coffee, Oligonychus ilicus (southern red mite), Panonychusspp., Panonychus citri (citrus red mite), Panonychus ulmi (European redmite), Phyllocoptruta oleivora (citrus rust mite), Polyphagotarsonemunlatus (broad mite), Rhipicephalus sanguineus (brown dog tick),Rhizoglyphus spp. (bulb mites), Sarcoptes scabiei (itch mite),Tegolophus perseaflorae, Tetranychus spp., Tetranychus urticae(twospotted spider mite), and Varroa destructor (honey bee mite).

In additional embodiments, the method of the present disclosure may beused to control members of the Order Nematoda (nematodes) including, butnot limited to, Aphelenchoides spp. (foliar nematodes), Belonolaimusspp. (sting nematodes), Criconemella spp. (ring nematodes), Dirofilariaimmitis (dog heartworm), Dilenchus spp. (stem and bulb nematodes),Heterodera spp. (cyst nematodes), Heterodera zeae (corn cyst nematode),Hirschmanniella spp. (root nematodes), Hoplolaimus spp. (lancenematodes), Meloidogyne spp. (root knot nematodes), Meloidogyneincognita (root knot nematode), Onchocerca volvulus (hook-tail worm),Pratylenchus spp. (lesion nematodes), Radopholus spp. (burrowingnematodes), and Rotylenchus reniformis (kidney-shaped nematode).

In at least some embodiments, the method of the present disclosure maybe used to control at least one insect in one or more of the OrdersLepidoptera, Coleoptera, Homoptera, Hemiptera, Thysanoptera, Isoptera,Orthoptera, Diptera, Hymenoptera, and Siphonaptera, and at least onemite in the Order Acari.

Insecticidal Testing

Example A Bioassay for Green Peach Aphid (GPA) (Myzus persicae) (MYZUPE)

The green peach aphid (Myzus persicae) is the most significant aphidpest of peach trees, causing decreased growth, shriveling of the leaves,and the death of various tissues. It is also hazardous because it actsas a vector for the transport of plant viruses, such as potato virus Yand potato leafroll virus to members of the nightshade/potato familySolanaceae, and various mosaic viruses to many other food crops. GPAattacks such plants as broccoli, burdock, cabbage, carrot, cauliflower,daikon, eggplant, green beans, lettuce, macadamia, papaya, peppers,sweet potatoes, tomatoes, watercress, and zucchini, among other plantsGPA also attacks many ornamental crops such as carnation, chrysanthemum,flowering white cabbage, poinsettia, and roses. GPA has developedresistance to many pesticides.

Cabbage seedlings grown in 3-inch pots, with 2-3 small (3-5 cm) trueleaves, were used as test substrate. The seedlings were infested with20-50 GPA (wingless adult and nymph stages) one day prior to chemicalapplication. Four pots with individual seedlings were used for eachtreatment. Test compounds (2 mg) were dissolved in 2 mL ofacetone/methanol (1:1) solvent, forming stock solutions of 1000 ppm testcompound. The stock solutions were diluted 5× with 0.025% Tween 20 inwater to obtain the solution at 200 ppm test compound. A hand-heldaspirator-type sprayer was used for spraying a solution to both sides ofcabbage leaves until runoff. Reference plants (solvent check) weresprayed with the diluent only containing 20% by volume ofacetone/methanol (1:1) solvent. Treated plants were held in a holdingroom for three days at approximately 25° C. and ambient relativehumidity (RH) prior to grading. Evaluation was conducted by counting thenumber of live aphids per plant under a microscope. Percent control wasmeasured by using Abbott's correction formula (W. S. Abbott, “A Methodof Computing the Effectiveness of an Insecticide” J. Econ. Entomol. 18(1925), pp. 265-267) as follows.Corrected % Control=100*(X−Y)/X

where

X=No. of live aphids on solvent check plants and

Y=No. of live aphids on treated plants

The results are indicated in the table entitled “Table 2. BiologicalData for Green Peach Aphid (GPA) (MYZUPE) and SweetpotatoWhitefly-Crawler (WF) (BEMITA)” (see table section).

Example B Insecticidal Test for Sweetpotato Whitefly-Crawler (WF)(Bemisia tabaci) (BEMITA) in Foliar Spray Assay

The sweetpotato whitefly (Bemisia tabaci) has been reported as a seriouspest of cultivated crops world-wide. It has an extremely wide host rangeattacking more than 500 species of plants from 63 plant families. Weedsoften serve as alternate hosts of crop pests. Direct feeding damage iscaused by the piercing and sucking sap from the foliage of plants. Thisfeeding causes weakening and early wilting of the plant and reduces theplant growth rate and yield Indirect damage results by the accumulationof honeydew produced by the whiteflies. Honeydew serves as a substratefor the growth of black sooty mold on leaves and fruit reducingphotosynthesis and lessens the market value of the plant or yield.Damage is also caused when sweetpotato whitefly vectors plant viruses.The sweetpotato whitefly is considered the most common and importantwhitefly vector of plant viruses worldwide.

Cotton plants (Gossypium hirsutum) grown in 3-inch pots, with 1 small(4-5 cm) true leaves, were used as test substrate. The plants wereinfested with 200-400 whitefly eggs 4-5 days prior to chemicalapplication. Four pots with individual plants were used for eachtreatment. Test compounds (2 mg) were dissolved in 1 mL of acetonesolvent, forming stock solutions of 2000 ppm test compound. The stocksolutions were diluted 10× with 0.025% Tween 20 in water (diluents) toobtain the solution at 200 ppm test compound. A hand-held aspirator-typesprayer was used for spraying a solution to both sides of cotton leavesuntil runoff. Reference plants (solvent check) were sprayed with thediluent only containing 10% by volume of acetone solvent. Treated plantswere held in a holding room for 9 days at approximately 25° C. andambient relative humidity (RH) prior to grading. Evaluation wasconducted by counting the number of live 3-4 nymph stage per plant undera microscope. Percent control was measured by using Abbott's correctionformula (W. S. Abbott, “A Method of Computing the Effectiveness of anInsecticide” J. Econ. Entomol. 18 (1925), pp. 265-267) as follows.

The results are indicated in the table entitled “Table 2. BiologicalData for Green Peach Aphid (GPA) (MYZUPE) and SweetpotatoWhitefly-Crawler (WF) (BEMITA)” (see table section).Corrected % Control=100*(X−Y)/X

where

X=No. of live nymphs on solvent check plants and

Y=No. of live nymphs on treated plants

Table 2 shows the pesticidal activities of the pesticidal compoundsagainst green peach aphid (GPA, MYZUPE) and sweetpotato whitefly-crawler(WF, BEMITA). The mortality efficiency of the pesticidal compoundsagainst GPA and WF insects was determined after treatment. The mortalityefficiency of the disclosed pesticidal compounds against GPA and WFinsects was rated as shown in Table 1.

TABLE 1 Mortality Rating for Green Peach Aphid (GPA) and Whitefly (WF) %Control (or Mortality) Rating 80-100 A More than 0-Less than 80 B NotTested C No activity noticed in this bioassay D

TABLE 2 Biological Data for Green Peach Aphid (MYZUPE) and SweetpotatoWhitefly-crawler (BEMITA) Insect Species GPA WF No. 200 ppm 200 ppm F1 AA F2 A A F3 A A F4 A A F5 A A F6 A A F7 B A F8 A A F9 A B F10 B A F11 BA F12 A A F13 B A F14 B A F15 B A F16 A A F17 B A F18 B A F19 A A F20 AA F21 B A F22 B A F23 B A F24 A A F25 B A F26 A B F27 B A F28 A A F29 AA F30 A A F31 A A F32 A A F33 B A F34 B A F35 A A F36 A A F37 B A F38 AA F39 A A F40 B B F41 C C F42 A A F43 B A F44 A A F45 C C F46 B A F47 CC F48 A A F49 A A F50 B A F51 A A F52 A A F53 A A F54 A A F55 B A F56 AA F57 A A F58 A A F59 A A F60 A A F61 A B F62 A A F63 A A F64 A A F65 AA F66 A A F67 A A F68 B A F69 A A F70 A A F71 A A F72 A A F73 A A F74 AA F75 A A F76 B B F77 A A F78 A A F79 B B F80 B A F81 A A F82 B A F83 AB F84 A A F85 A A F86 A A F87 C C F88 B A F89 A A F90 B A F91 A A F92 AA F93 A A F94 A A F95 B B F96 A A F97 A A F98 A A F99 B A F100 B A F101B A F102 A A F103 A A F104 A A F105 B A F106 B B F107 A A F108 A A F109B A F110 A A F111 A A F112 B A F113 A A F114 A A F115 B A F116 B A F117A A F118 A A F119 A A F120 A A F121 A A F122 B A F123 B A F124 A A F125A A F126 B A F127 B A F128 A A F129 B A F130 A A F131 A A C1 D B C2 B AC3 B C C4 B C C5 B D C10 A A C11 B A C12 A A C13 A A C14 A A P1 A A P16A B P20 A B P21 A B P23 A A P24 A B FA1 B A FA2 B A FA3 A A FA4 B A FA5A B FA6 A B FA7 A D FA8 A B FA9 A D FA10 A A FA11 A A FA12 B B FA13 C CFA14 A A FA15 A A FA16 B B FA17 B B FA18 A A FA19 B A FA20 A A FA21 B CFA22 B A FA23 B C FA24 B C FA25 B C FA26 B A FA27 B B FA28 B B FA29 B AFA30 D B FA31 D B FA32 B B FA33 A A FA34 A A FA35 B A FA36 B B FA37 B AFA38 B B FA39 B B FA40 B A FA41 A B FA42 A B FA43 A A FA44 A A FA45 A BFA46 B A FA47 C C FA48 C C FA49 B A FA50 A A FA51 C C FA52 C C FA53 C CFA54 C C FA55 C C FA56 C C FA57 A B FA58 A C FA59 A A FA60 A A FA61 A AFA62 A A FA63 A A FA64 A A FA65 A A FA66 A A FA67 C C FA68 D A FA69 B AFA70 B A FA71 B B FA72 B A FA73 A B FA74 A B FA75 B A FA76 B A FA77 B ACA1 A C CA2 B A CA3 C C

The following examples serve to explain embodiments of the presentinvention in more detail. These examples should not be construed asbeing exhaustive or exclusive as to the scope of this invention.

EXAMPLES

These examples are for illustration purposes and are not to be construedas limiting the disclosure to only the embodiments disclosed in theseexamples.

Starting materials, reagents, and solvents that were obtained fromcommercial sources were used without further purification. Anhydroussolvents were purchased as SURE/SEAL™ from Aldrich and were used asreceived. Melting points were obtained on a Thomas Hoover Unimeltcapillary melting point apparatus or an OptiMelt Automated Melting PointSystem from Stanford Research Systems and are uncorrected. Examplesusing “room temperature” were conducted in climate controlledlaboratories with temperatures ranging from about 20° C. to about 24° C.Molecules are given their known names, named according to namingprograms within ISIS Draw, ChemDraw or ACD Name Pro. If such programsare unable to name a molecule, the molecule is named using conventionalnaming rules. ¹H NMR spectral data are in ppm (δ) and were recorded at300, 400 or 600 MHz. ¹³C NMR spectral data are in ppm (δ) and wererecorded at 75, 100 or 150 MHz. ¹⁹F NMR spectral data are in ppm (δ) andwere recorded at 376 MHz, unless otherwise stated.

Example 1 Preparation ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-(cyclopropylmethyl)-2-(2-oxopyrrolidin-1-yl)acetamide

To a 7 mL vial was added3-chloro-N-(cyclopropylmethyl)-1-(pyridin-3-yl)-1H-pyrazol-4-amine(0.124 g, 0.500 mmol) (prepared according to the U.S. Publication No.2012/0110702), DMAP (0.183 g, 1.50 mmol), 2-(2-oxopyrrolidin-1-yl)aceticacid (0.143 g, 1.00 mmol), EDCI (0.240 g, 1.25 mmol) followed by CH₂Cl₂(1 mL). The reaction mixture was stirred at a temperature of about 25°C. for 18 hours before it was purified by silica gel chromatography(0%-15% MeOH/CH₂Cl₂) to afford the title compound F98 as a light yellowoil (0.131 g, 70%).

The following molecules were made in accordance with the proceduresdisclosed in example 1:

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-methyl-2-(2-oxopyrrolidin-1-yl)acetamide(Compound F6) was isolated as an off-white solid (0.167 g, 100%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-2-(2-oxopyrrolidin-1-yl)acetamide(Compound F124) was isolated as a light yellow oil (0.169 g, 97%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-methyl-2-(2-oxopyridin-1(2H)-yl)acetamide(Compound F3) was isolated as a white semi-solid (0.056 g, 33%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-2-(2-oxopyridin-1(2H)-yl)acetamide(Compound F122) was isolated as a white semi-solid (0.054 g, 30%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-methyl-4-oxo-4-(piperidin-1-yl)butanamide(Compound F33) was isolated as a white solid (0.181 g, 95%).

4-(Azepan-1-yl)-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-methyl-4-oxobutanamide(Compound F27) was isolated as a white solid (0.188 g, 96%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-methyl-4-oxo-4-(pyrrolidin-1-yl)butanamide(Compound F37) was isolated as a white solid (0.180 g, 99%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-4-oxo-4-(piperidin-1-yl)butanamide(Compound F21) was isolated as an off-white solid (0.192 g, 98%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-(cyclopropylmethyl)-4-oxo-4-(piperidin-1-yl)butanamide(Compound F82) was isolated as an off-white-solid (0.140 g, 67%).

4-(Azepan-1-yl)-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-4-oxobutanamide(Compound F100) was isolated as an off-white solid (0.181 g, 90%).

4-(Azepan-1-yl)-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-(cyclopropylmethyl)-4-oxobutanamide(Compound F18) was isolated as an off-white solid (0.167 g, 78%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-4-oxo-4-(pyrrolidin-1-yl)butanamide(Compound F106) was isolated as a light yellow semi-solid (0.125 g,67%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-(cyclopropylmethyl)-4-oxo-4-(pyrrolidin-1-yl)butanamide(Compound F95) was isolated as a light yellow solid (0.130 g, 65%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-methyl-2-(2-oxopiperidin-1-yl)acetamide(Compound F77) was isolated as an off-white solid (0.062 g, 36%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-2-(2-oxopiperidin-1-yl)acetamide(Compound F47) was isolated as an off-white solid (0.045 g, 25%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-methyl-2-(2-oxoazepan-1-yl)acetamide(Compound F22) was isolated as an off-white solid (0.162 g, 90%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-2-(2-oxoazepan-1-yl)acetamide(Compound F123) was isolated as a light yellow semi-solid (0.152 g,81%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-(2-oxooxazolidin-3-yl)propanamide(Compound 69) was isolated as a colorless semi-solid (0.178 g, 98%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-methyl-2-(2-oxooxazolidin-3-yl)acetamide(Compound F111) was isolated as a white solid (0.150 g, 89%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-2-(2-oxooxazolidin-3-yl)acetamide(Compound F48) was isolated as a white solid (0.119 g, 68%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-methyl-2-(2-oxothiazolidin-3-yl)acetamide(Compound F7) was isolated as a white solid (0.166 g, 94%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-2-(2-oxothiazolidin-3-yl)acetamide(Compound F10) was isolated as a white solid (0.146 g, 80%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-methyl-3-(2-oxopyrrolidin-1-yl)propanamide(Compound F107) was isolated as a colorless semi-solid (0.167 g, 96%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-(2-oxopyrrolidin-1-yl)propanamide(Compound F39) was isolated as a colorless oil (0.147 g, 81%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-methyl-3-(2-oxopiperidin-1-yl)propanamide(Compound F49) was isolated as a colorless oil (0.193 g, 96%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-(2-oxopiperidin-1-yl)propanamide(Compound F8) was isolated as a white solid (0.155 g, 82%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-(2-oxothiazolidin-3-yl)propanamide(Compound F88) was isolated as a colorless oil (0.091 g, 48%).

1-Acetyl-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-methylpiperidine-4-carboxamide(Compound F29) was isolated as a white semi-solid (0.206 g, 85%).

1-Acetyl-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethylpiperidine-4-carboxamide(Compound F61) was isolated as a white semi-solid (0.217 g, 87%).

tert-Butyl(3-((3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)amino)-3-oxopropyl)(methyl)carbamate (Compound F52) was isolated as a colorless oil (0.192 g, 75%).

tert-Butyl 44-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethylcarbamoyl) piperidine-1-carboxylate (Compound F110) was isolated as awhite semi-solid (2 g, 77%).

tert-Butyl 3-((3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)carbamoyl azetidine-1-carboxylate (Compound F26) was isolated as a whitesemi-solid (2 g, 82%).

tert-Butyl(2-((3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(methyl)amino)-2-oxoethyl)(methyl)carbamate (Compound F90) was isolated as a colorless oil (2 g, 73%).

tert-Butyl(2-((3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)amino)-2-oxoethyl)(methyl)carbamate (Compound F4) was isolated as a colorless oil(0.616 g, 87%).

tert-Butyl(2-((3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(cyclopropylmethyl)amino)-2-oxoethyl)(methyl)carbamate (Compound F76) was isolated as a white semi-solid(0.642 g, 95%).

tert-Butyl(2-((3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(prop-2-yn-1-yl)amino)-2-oxoethyl)(methyl)carbamate (Compound F23) was isolated as a white solid (0.513 g, 74%).

1-Acetyl-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethylpyrrolidine-3-carboxamide(Compound P20) was isolated as a white solid (0.202 g, 88%).

1-Acetyl-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethylazetidine-3-carboxamide(Compound P23) was isolated as a white solid (0.162 g, 74%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-1-isobutylylpiperidine-3-carboxamide(Compound FA3) was isolated as a white semi-solid (0.216 g, 80%).

tert-Butyl2-((3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)carbamoyl)piperidine-1-carboxylate (Compound FA13) was isolated as a whitesemi-solid (0.123 g, 28%).

tert-Butyl3-((3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)carbamoyl)piperidine-1-carboxylate (Compound FA18) was isolated as a yellowsemi-solid (1.08 g, 45%).

1-Acetyl-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethylpiperidine-2-carboxamide(Compound FA32) was isolated as a yellow oil (0.121 g, 61%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-4-(2-oxopyrrolidin-1-yl)butanamide(Compound FA33) was isolated as a yellow oil (0.151 g, 72%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-4-(2-oxooxazolidin-3-yl)butanamide(Compound FA34) was isolated as a yellow oil (0.148 g, 71%).

N-methyl-N-(3-methyl-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-4-oxopentanamide(Compound FA69) was isolated as a colorless oil (0.114 g, 75%).

N-Ethyl-N-(1-(5-fluoropyridin-3-yl)-3-methyl-1H-pyrazol-4-yl)-5-oxohexanamide(Compound FA70) was isolated as a colorless oil (0.119 g, 79%).

N-Ethyl-N-(1-(5-fluoropyridin-3-yl)-3-methyl-1H-pyrazol-4-yl)-3-oxocyclopentanecarboxamide(Compound FA71) was isolated as a tan solid (0.1 g, 62%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-7,7,7-trifluoro-4-oxoheptanamide(Compound FA76) was isolated as a brown viscous oil (0.059 g, 50%).

N-[3-Chloro-1-(3-pyridyl)pyrazol-4-yl]-N-ethyl-2-methyl-pent-4-enamide(Compound CA1) was isolated as a clear, colorless oil (0.502 g, 75%): ¹HNMR (400 MHz, CDCl₃) δ 8.94 (dd, J=2.7, 0.8 Hz, 1H), 8.63 (dd, J=4.8,1.5 Hz, 1H), 8.05 (ddd, J=8.3, 2.8, 1.5 Hz, 1H), 7.91 (s, 1H), 7.46(ddd, J=8.4, 4.8, 0.8 Hz, 1H), 5.75-5.59 (m, 1H), 5.07-4.97 (m, 2H),3.69 (d, J=47.8 Hz, 2H), 2.44 (ddt, J=28.2, 14.3, 7.2 Hz, 2H), 2.07(tdd, J=7.5, 6.2, 5.0 Hz, 1H), 1.15 (t, J=7.2 Hz, 3H), 1.09 (d, J=6.6Hz, 3H); ESIMS m/z 319 ([M+H]⁺).

Example 2 Preparation ofN1,N1,N4-trimethyl-N4-(3-methyl-1-(pyridin-3-yl)-1H-pyrazol-4-yl)succinamide

To an ice cold solution of 4-(dimethylamino)-4-oxobutanoic acid (0.174g, 1.20 mmol) in CH₂Cl₂ (2 mL) was added DIPEA (0.208 mL, 1.120 mmol)followed by isobutyl chloroformate (0.138 mL, 1.06 mmol). The mixturewas stirred for 10 minutes, and the resulting mixed anhydride was addedto a solution of N,3-dimethyl-1-(pyridin-3-yl)-1H-pyrazol-4-amine (0.100g, 0.531 mmol) in CH₂Cl₂ (0.66 mL). The reaction mixture was stirred atroom temperature (about 22° C.) for one hour. The crude reaction mixturewas concentrated and purified via reverse phase column chromatography(0%-100% acetonitrile (MeCN)/water) to give the desired product F62 as awhite solid (0.155 g, 83%).

The following molecules were made in accordance with the proceduresdisclosed in example 2:

N1-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N1,N4,N4-trimethylsuccinimide (Compound F25) was isolated as a white solid (0.122 g, 68%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-methyl-4-oxopentanamide(FA75) was isolated as a brown solid (1.26 g, 58%).

Example 3 Preparation of4-((3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)amino)-4-oxobutanoicacid

To a 100 mL round-bottomed flask with a stir bar was added3-chloro-N-ethyl-1-(pyridin-3-yl)-1H-pyrazol-4-amine (0.500 g, 2.25mmol), DMAP (0.0274 g, 0.225 mmol), triethylamine (0.469 mL, 3.37 mmol),and dihydrofuran-2,5-dione (0.449 g, 4.49 mmol) with DCE (22.5 mL).After heating at a temperature of about 60° C. under nitrogen (N2)overnight, the reaction mixture was concentrated and purified by silicagel flash column chromatography eluting with 0%-15% MeOH/CH₂Cl₂ toafford the title compound C1 as an off-white solid (0.635 g, 86%): IR(thin film) 3097, 1661 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 9.00 (s, 1H),8.59 (d, J=4.8 Hz, 1H), 8.15 (ddd, J=8.4, 2.6, 1.4 Hz, 1H), 8.12 (s,1H), 7.49 (dd, J=8.4, 4.8 Hz, 1H), 3.72 (q, J=7.2 Hz, 2H), 3.49 (s, 1H),2.72 (d, J=10.6 Hz, 2H), 2.47 (t, J=6.4 Hz, 2H), 1.16 (t, J=7.2 Hz, 3H);ESIMS m/z 323 ([M+H]⁺).

Example 4 Preparation ofN1-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N1-ethyl-N4-methyl-N4-(3,3,3-trifluoropropyl)succinamide

A solution of4-((3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)amino)-4-oxobutanoicacid (0.100 g, 0.310 mmol), DMAP (0.129 g, 1.05 mmol), and3,3,3-trifluoro-N-methylpropan-1-amine (0.0394 g, 0.310 mmol) in dryCH₂Cl₂ (1.0 mL) was cooled to a temperature of about 0° C. under N₂.N,N′-Methanediylidenedicyclohexanamine (0.153 mg, 0.744 mmol) was added,and the reaction was slowly warmed up to room temperature under N2, thenstirred at room temperature overnight. The reaction mixture was filteredusing additional CH₂Cl₂ (0.5 mL) to remove solids and concentrated underreduced pressure. The residue was purified by silica gel chromatographyeluting with 0%-5% MeOH/CH₂Cl₂ to afford the title compound F108 as aclear viscous oil (0.078 g, 57%).

The following molecules were made in accordance with the proceduresdisclosed in example 4:

N1-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N1-ethyl-N4-(3,3,3-trifluoropropyl)succinamide (Compound F73) was isolated as a clear foam (0.389 g, 76%).

N1-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N1-ethyl-N4-methoxy-N4-methylsuccinamide(Compound F78) was isolated as a white semi-solid (0.307 g, 65%).

N1-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N4-(cyclohexylmethyl)-N1-ethylsuccinamide(Compound F15) was isolated as a light yellow solid (0.048 g, 52%).

N1-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N1-ethyl-N4-((5-methylfuran-2-yl)methyl)succinamide(Compound F13) was isolated as a slightly yellow solid (0.072 g, 64%).

N1-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N1-ethyl-N4-(pyridin-4-ylmethyl)succinamide(Compound F115) was isolated as a light yellow solid (0.076 g, 64%).

N1-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N4-(3-chlorobenzyl)-N1-ethylsuccinamide(Compound F68) was isolated as a viscous slightly cloudy oil (0.083 g,71%).

N1-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N1-ethyl-N4-(4-fluorobenzyl)-N4-methylsuccinamide(Compound F118) was isolated as a cloudy white viscous semi-solid (0.041g, 36%).

N1-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N4-(cyclopropylmethyl)-N1-ethyl-N4-methylsuccinamide(Compound F30) was isolated as a light yellow clear viscous oil (0.069g, 70%).

N1-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N4-(cyclopropylmethyl)-N1-ethylsuccinamide(Compound F70) was isolated as a white semi-solid (0.037 g, 38%).

N1-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N1-ethyl-N4-(4-fluorobenzyl)succinamide(Compound F80) was isolated as a white solid (0.087 g, 79%).

N1-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N4-(cyanomethyl)-N1-ethyl-N4-methylsuccinamide(Compound F55) was isolated as a brown viscous semi-solid (0.066 g,67%).

N1-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N1-ethyl-N4-(2,2,2-trifluoroethyl)succinamide(Compound F67) was isolated as a white solid (0.064 g, 61%).

N1-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N1-ethyl-N4-(2-fluoroethyl)succinamide(Compound F43) was isolated as a clear semi-solid (0.070 g, 74%).

N1-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N1-ethyl-N4-(2-(trifluoromethyl)cyclopropyl)succinamide (Compound F54) was isolated as a white semi-solid (0.036 g,31%).

N1-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N1-ethyl-N4-methyl-N4-(2,2,2-trifluoroethyl)succinamide (Compound F85) was isolated as a light brown viscoussemi-solid (0.086 g, 80%).

N1-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N1-ethyl-N4-(furan-2-ylmethyl)-N4-methylsuccinamide(Compound FA77) was isolated as an orange oil (0.074 g, 69%).

Example 5 Preparation ofN-(2-((3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)amino)-2-oxoethyl)-N-methylbenzamide

A solution of 3-chloro-N-ethyl-1-(pyridin-3-yl)-1H-pyrazol-4-amine(0.075 g, 0.34 mmol), 2-(N-methylbenzamido)acetic acid (0.098 g, 0.51mmol), and DMAP (0.062 g, 0.51 mmol) in dry diethyl ether (1.0 mL) anddry CH₂Cl₂ (1.1 mL) was cooled to a temperature of about 0° C. under N2.DCC (0.17 g, 0.81 mmol) was added, and the reaction was slowly warmed upto room temperature under N2, then stirred at room temperatureovernight. The reaction mixture was filtered using additional CH₂Cl₂(0.5 mL) to remove solids and concentrated under reduced pressure. Theresidue was purified by silica gel chromatography eluting with 0%-10%MeOH/CH₂Cl₂ to afford the title compound F83 as a white solid (0.12 g,87%).

The following molecules were made in accordance with the proceduresdisclosed in example 5:

tert-Butyl(3-((3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)amino)-3-oxopropyl)carbamate(Compound F19) was isolated as a white solid (1.506 g, 83%).

tert-Butyl(2-((3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)amino)-2-oxoethyl)carbamate(Compound F2) was isolated as a pink solid (1.256 g, 71%).

Example 6 Preparation of3-amino-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethylpropanamide

To a solution of tert-butyl(3-((3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)amino)-3-oxopropyl)carbamate (0.100 g, 0.254 mmol) in dry CH₂Cl₂(0.254 mL, 0.254 mmol), TFA (0.254 mL, 0.254 mmol) was added at roomtemperature under N2. The reaction was stirred at room temperature forabout 2 hours. Saturated aqueous sodium bicarbonate (NaHCO₃) (about 5mL) was carefully added until reaction mixture became basic. Thereaction product was extracted with CH₂Cl₂ (3×5 mL), dried andconcentrated. Crude product was generally used without purification inmost cases. The product can be purified by reverse phase silica gelchromatography eluting with 10%-100% MeCN/water to afford the titlecompound C2 as a viscous light yellow oil (0.0160 g, 22%): IR (thinfilm) 3368, 3091, 1657 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 8.95 (dd, J=2.8,0.8 Hz, 1H), 8.62 (dd, J=4.7, 1.5 Hz, 1H), 8.04 (ddd, J=8.3, 2.7, 1.4Hz, 1H), 7.98 (s, 1H), 7.46 (ddd, J=8.3, 4.7, 0.8 Hz, 1H), 3.71 (q,J=7.2 Hz, 2H), 2.97 (t, J=6.1 Hz, 2H), 2.32 (t, J=6.1 Hz, 2H), 1.72 (s,2H), 1.16 (t, J=7.2 Hz, 3H); HRMS-FAB (m/z) ([M+H]⁺) calc'd forC₁₃H₁₇ClN₅₀, 294.1116; found, 294.1117.

Example 7 Preparation ofN-(3-((3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)amino)-3-oxopropyl)-2,2-difluoro-1-methylcyclopropanecarboxamide

A solution of3-amino-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethylpropanamide(0.074 mg, 0.25 mmol), DMAP (0.047 mg, 0.38 mmol),2,2-difluoro-1-methylcyclopropanecarboxylic acid (0.052 mg, 0.38 mmol)in dry CH₂Cl₂ (1.69 mL) was cooled to a temperature of about 0° C. underN2. DCC (0.13 g, 0.61 mmol) was added, and the reaction was slowlywarmed up to room temperature under N2, then stirred at room temperatureovernight. The reaction mixture was filtered using additional CH₂Cl₂(0.5 mL) to remove solids and concentrated under reduced pressure. Theproduct was purified by silica gel chromatography eluting with 0%-10%MeOH/CH₂Cl₂ to afford the title compound F113 as a yellow viscous oil(0.029 g, 26% over 2 steps from compound C2).

The following molecules were made in accordance with the proceduresdisclosed in example 7:

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-3-(2-cyclopropylacetamido)-N-ethylpropanamide(Compound F75) was isolated as a white hard sticky foam (0.090 g, 84%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-(2-(4-fluorophenyl)acetamido) propanamide (Compound F46) was isolated as a white solid(0.066 g, 83%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-3-(2-cyanoacetamido)-N-ethylpropanamide(Compound F101) was isolated as a light yellow solid (0.075 g, 83%).

(E)-N-(3-((3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)amino)-3-oxopropyl)-4,4,4-trifluorobut-2-enamide(Compound F65) was isolated as a brown solid (0.026 g, 24% over twosteps from compound C2).

N-(3-((3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)amino)-3-oxopropyl)-4,4,4-trifluoro-2-methylbutanamide(Compound F44) was isolated as an off-white foam (0.050 g, 37% over twosteps from compound C2).

N-(2-((3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)amino)-2-oxoethyl)-2,2-difluoro-1-methylcyclopropanecarboxamide(Compound F1) was isolated as a white solid (0.055 g, 41% over two stepsfrom compound C2).

(E)-N-(2-((3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)amino)-2-oxoethyl)-4,4,4-trifluorobut-2-enamide(Compound F99) was isolated as an orange oil (0.061 g, 46% over twosteps from compound C2).

N-(3-((3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)amino)-3-oxopropyl)-2,2-difluorocyclopropanecarboxamide(Compound F56) was isolated as a light brown solid (0.045 g, 35% overtwo steps from compound C2).

N-(3-((3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)amino)-3-oxopropyl)-4,4,4-trifluoro-3-methylbutanamide(Compound F28) was isolated as an off-white foam (0.044 g, 33% over twosteps from compound C2).

N-(3-((3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)amino)-3-oxopropyl)-4,4,4-trifluorobutanamide(Compound F12) was isolated as an off-white semi-solid (0.044 g, 33%over two steps from compound C2).

N-(2-((3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)amino)-2-oxoethyl)-4,4,4-trifluorobutanamide(Compound F97) was isolated as an off-white solid (0.080 g, 61% over twosteps from compound C2).

N-(3-((3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)amino)-3-oxopropyl)-4,4,4-trifluoro-N-methylbutanamide(Compound F94) was isolated as a viscous clear oil (0.083 g, 81%).

N-(2-((3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)amino)-2-oxoethyl)-4,4,4-trifluoro-N-methylbutanamide(Compound F5) was isolated as a light yellow foam (0.076 g, 75%).

1-Acetyl-N-(3-((3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)amino)-3-oxopropyl)piperidine-4-carboxamide(Compound F112) was isolated as a white foam (35 mg, 19% over two stepsfrom compound C11).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-3-(N-cyclopropylacetamido)-N-ethylpropanamide(Compound F9) was isolated as a yellow oil (0.074 g, 59%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-1-(3,3,3-trifluoropropanoyl)piperidine-4-carboxamide(Compound P16) was isolated as a white semi-solid (0.154 g, 81%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-1-(3,3,3-trifluoropropanoyl)pyrrolidine-3-carboxamide(Compound P21) was isolated as a white semi-solid (0.13 g, 58%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-1-(3,3,3-trifluoropropanoyl)azetidine-3-carboxamide(Compound P24) was isolated as a colorless oil (0.11 g, 50%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-1-(2,2,2-trifluoroacetyl)piperidine-4-carboxamide(Compound FA5) was isolated as a white solid (0.069 g, 31%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-1-(4,4,4-trifluorobutanoyl)piperidine-4-carboxamide(Compound FA6) was isolated as a yellow solid (0.158 g, 66%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-1-(3-cyanopropanoyl)-N-ethylpiperidine-4-carboxamide(Compound FA7) was isolated as a yellow solid (0.199 g, 55%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-1-nicotinoylpiperidine-4-carboxamide(Compound FA8) was isolated as a white semi-solid (0.138 g, 60%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-1-(2,2,2-trifluoroacetyl)pyrrolidine-3-carboxamide(Compound FA9) was isolated as a colorless oil (0.074 g, 34%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-1-(4,4,4-trifluorobutanoyl)pyrrolidine-3-carboxamide(Compound FA10) was isolated as a white semi-solid (0.138 g, 59%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-1-(3-cyanopropanoyl)-N-ethylpyrrolidine-3-carboxamide(Compound FA11) was isolated as a yellow semi-solid (0.113 g, 51%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-1-nicotinoylpyrrolidine-3-carboxamide(Compound FA12) was isolated as a colorless oil (0.14 g, 59%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-1-(2,2,2-trifluoroacetyl)azetidine-3-carboxamide(FA14) was isolated as a colorless oil (0.122 g, 58%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-1-(4,4,4-trifluorobutanoyl)azetidine-3-carboxamide(FA15) was isolated as a colorless oil (0.135 g, 60%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-1-(3-cyanopropanoyl)-N-ethylazetidine-3-carboxamide(FA16) was isolated as a white solid (0.097 g, 48%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-1-nicotinoylazetidine-3-carboxamide (FA17) was isolated as a colorless oil (0.136 g,63%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-1-(2,2,2-trifluoroacetyl)piperidine-3-carboxamide(Compound FA41) was isolated as a white semi-solid (0.057 g, 25%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-1-(3,3,3-trifluoropropanoyl)piperidine-3-carboxamide(Compound FA42) was isolated as a white semi-solid (0.13 g, 56%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-1-(4,4,4-trifluorobutanoyl)piperidine-3-carboxamide(Compound FA43) was isolated as a yellow semi-solid (0.178 g, 74%).

N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-1-(3-cyanopropanoyl)-N-ethylpiperidine-3-carboxamide(Compound FA44) was isolated as a white semi-solid (0.148 g, 68%).

1-Acetyl-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethylpiperidine-3-carboxamide(Compound FA45) was isolated as a yellow solid (0.087 g, 44%).

N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-oxobutanamide(Compound FA66) was isolated as a yellow oil (0.151 g, 44%).

Example 8 Preparation ofN-(3-((3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)amino)-3-oxopropyl)-3,3,3-trifluoro-N-methylpropanamide

A solution ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-(methylamino)propanamide (0.070 g, 0.23 mmol) in dry CH₂Cl₂ (0.76 mL) wascooled to a temperature of about 0° C. under N2. To the solution, DMAP(0.014 g, 0.11 mmol), pyridine (0.028 mL, 0.34 mmol), and3,3,3-trifluoropropanoyl chloride (0.026 mL, 0.25 mmol) were addedsequentially. The reaction was slowly warmed up to room temperatureunder N2, then stirred at room temperature overnight. The reaction wasdiluted with water (2 mL) and stirred for five minutes. Layers wereseparated, and the aqueous layer was extracted with CH₂Cl₂ (2×2 mL). Thecombined organic extracts were dried and concentrated under reducedpressure. The residue was purified by silica gel chromatography elutingwith 0%-5% MeOH/CH₂Cl₂ to afford the title compound F102 as a whitesemi-solid (0.062 g, 63%).

The following molecules were made in accordance with the proceduresdisclosed in example 8:

N-(3-((3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)amino)-3-oxopropyl)-3,3,3-trifluoropropanamide(Compound F63) was isolated as a white solid (0.039 g, 31% over 2 stepsfrom compound C2).

N-(2-((3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)amino)-2-oxoethyl)-3,3,3-trifluoropropanamide(Compound F57) was isolated as a white solid (66 mg, 52% over 2 stepsfrom compound C2).

N-(2-((3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)amino)-2-oxoethyl)-3,3,3-trifluoro-N-methylpropanamide(Compound F120) was isolated as a white solid (0.057 g, 54%).

2-((3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)amino)-2-oxoethylacetate (Compound FA72) was isolated as a white solid (0.068 g, 27%).

1-((3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)amino)-2-methyl-1-oxopropan-2-ylacetate(Compound FA73) was isolated as an off-white solid (0.173 g, 73%).

1-((3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)amino)-1-oxopropan-2-yl3,3,3-trifluoropropanoate (Compound FA74) was isolated as a yellow oil(0.087 g, 63%).

Example 9 Preparation of tert-butyl3-(3-((3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)amino)-3-oxopropyl)-2-oxopyrrolidine-1-carboxylate

A solution of tert-butyl 2-oxopyrrolidine-1-carboxylate (1.24 mL, 1.35mmol) in dry THF (3.86 mL) was cooled to a temperature of about −78° C.under N2 using acetone/dry ice bath. A 1M THF solution of LiHMDS (1.62mL, 1.62 mmol) was added, and the reaction was stirred at a temperatureof about −78° C. for 45 minutes. To the mixture, a solution of3-chloro-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethylpropanamide(0.465 g, 1.49 mmol) in THF (3.86 mL) was added dropwise and stirred ata temperature of about −78° C. for 1 hour. The reaction was allowed towarm up to room temperature slowly and stirred overnight. The reactionmixture was quenched with saturated aqueous ammonium chloride (NH₄Cl, 5mL), and the product was extracted with CH₂Cl₂ (3×5 mL), dried andconcentrated. The residue was purified by silica gel chromatography byeluting with 20%-100% EtOAc/hexanes to afford the title compound F128 asa white foam (0.0770 g, 12%).

Example 10 Preparation ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-(2-oxopyrrolidin-3-yl)propanamide

To a solution of tert-butyl3-(3-((3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)amino)-3-oxopropyl)-2-oxopyrrolidine-1-carboxylate(0.076 g, 0.17 mmol) in dry CH₂Cl₂ (0.33 mL), TFA (0.33 mL) was added atroom temperature under N2. The reaction was stirred at room temperaturefor about 90 minutes. Saturated aqueous NaHCO₃ (about 10 mL) wascarefully added until reaction mixture became basic. The product wasextracted with CH₂Cl₂ (3×10 mL), dried and concentrated. The residue waspurified by silica gel chromatography by eluting with 0%-15% MeOH/CH₂Cl₂to afford the title compound F131 as a white foam (0.041 g, 66%).

Example 11 Preparation of tert-butyl(3-((3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)amino)-3-oxopropyl)(methyl)carbamate

To a clean vial with a stir bar tert-butyl(3-((3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)amino)-3-oxopropyl)carbamate(1.5 g, 3.8 mmol) was added and sealed with a septum cap. The headspacewas purged with N2, dry DMF (5.4 mL) was added via a syringe, and thereaction was cooled to a temperature of about 0° C. in an ice bath underN2. NaH (60% dispersion in oil, 0.21 g, 5.3 mmol) was carefully addedand stirred at a temperature of 0° C. for 30 minutes. Methyl iodide(0.29 mL, 4.6 mmol) was then added and stirred for 30 minutes at atemperature of 0° C. With the addition of methyl iodide, reaction becamelight yellow slurry. The reaction was warmed up to room temperature andstirred for 2 hours. As reaction warmed up, it turned to bright orangecolor. The reaction was quenched by the slow addition of water (100 mL).The suspension was vigorously stirred at room temperature for 2 hours.The water was filtered off, and remaining slurry was washed withhexanes. The slurry was then dissolved in methanol and passed throughthe filter. The resulting solution was concentrated, dried under highvacuum to afford brown, viscous oil (1.6 g, 78%).

Example 12 Preparation of2-(1-(tert-butyldimethylsilyl)-2-oxoacetidin-3-yl)acetic acid

A stirred solution of 3-allyl-1-(tert-butyldimethylsilyl)azetidin-2-one(4.90 g, 22.2 mmol) in a mixture of carbontetrachloride(CCl₄)/MeCN/water (50 mL/50 mL/100 mL) was charged withsodium periodate (18.9 g, 88.7 mmol) followed by ruthenium (III)chloride trihydrate (0.114 g, 0.440 mmol) at room temperature andstirred for 3 hours. The reaction mixture was diluted with water (100mL) and extracted with CH₂Cl₂ (3×100 mL). The combined organic layerswere dried over sodium sulfate (Na₂SO₄), filtered and concentrated underreduced pressure to afford the title compound C3 as a black semi solid(4.58 g, 85%): IR (KBr) 2956, 2929, 2351, 1732, 1681, 1361, 1215 cm⁻¹;¹H NMR (400 MHz, CDCl₃) δ 3.62-3.59 (m, 1H), 3.46 (t, J=6.0 Hz, 1H),3.05 (dd, J=6.4 Hz, 2.8 Hz, 1H), 2.88 (dd, J=17.2 Hz, 5.6 Hz, 1H), 2.67(dd, J=17.2 Hz, 10.0 Hz, 1H), 0.96 (s, 9H), 0.25 (s, 3H), 0.23 (s, 3H);ESIMS m/z 244 ([M+H]⁺).

The following molecules were made in accordance with the proceduresdisclosed in example 12:

3-(1-(tert-Butyldimethylsilyl)-2-oxoazetidin-3-yl)propanoic acid(Compound C4) was isolated as a black semi solid (5.07 g, 89%): IR (KBr)2929, 2858, 2376, 1718, 1695, 1345, 1219 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ3.37-3.32 (m, 2H), 2.93-2.91 (m, 1H), 2.56-2.48 (m, 2H), 2.10-1.97 (m,2H), 0.95 (s, 9H), 0.25 (s, 3H), 0.23 (s, 3H); ESIMS m/z 258 ([M+H]⁺).

4-(1-(tert-Butyldimethylsilyl)-2-oxoazetidin-3-yl)butanoic acid(Compound C5) was isolated as a black semi solid (5.17 g, 86%): IR(KBr): 2954, 2858, 2358, 1728, 1467, 1350, 1199 cm⁻¹; ¹H NMR (400 MHz,CDCl₃) δ 3.37-3.28 (m, 2H), 2.93 (dd, J=2.8 Hz, 6.0 Hz, 1H), 2.43 (t,J=6.8 Hz, 2H), 1.89-1.66 (m, 4H), 0.97 (s, 9H), 0.25 (s, 3H), 0.23 (s,3H); ESIMS m/z 272 ([M+H]⁺).

Example 13 Preparation ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-2-(2-oxoazetidin-3-yl)acetamide

A stirred solution of2-(1-(tert-butyldimethylsilyl)-2-oxoacetidin-3-yl)acetic acid (4.10 g,16.9 mmol) and 3-chloro-N-ethyl-1-(pyridin-3-yl)-1H-pyrazol-4-amine(2.48 g, 11.2 mmol) in EtOAc (50 mL) was charged with triethylamine(6.24 mL, 44.8 mmol) followed by n-propanephosphonic acid anhydride(T3P®) (50% in DMF, 22.5 mmol) at room temperature. The resultantreaction mixture was heated at reflux for 3 hours. The reaction mixturewas diluted with water (50 mL) and extracted with EtOAc (3×100 mL). Thecombined organic layers were washed with brine solution (100 mL), driedover Na₂SO₄, filtered and concentrated under reduced pressure. Theresidue was purified by flash chromatography eluting with 1%-10%MeOH/CH₂Cl₂ to afford the title compound F71 as an off white solid (1.60g, 43%).

The following molecules were made in accordance with the proceduresdisclosed in example 13:

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-(2-oxoazetidin-3-yl)acetamide(Compound F50) was isolated as a light yellow gum (1.7 g, 45%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-4-(2-oxoazetidin-3-yl)acetamide(Compound F58) was isolated as a light yellow gum (2.5 g, 63%).

Example 14 Preparation ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-2-(1-methyl-2-oxoazetidin-3-yl)acetamide

To a suspension of NaH (60% dispersion in oil, 0.029 g, 0.72 mmol) inDMF (2 mL) was addedN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-2-(2-oxoazetidin-3-yl)acetamide(0.20 g, 0.60 mmol) in DMF (0.5 mL), dropwise, at a temperature of about−10° C. over one minute. The reaction mixture was charged with methyliodide (0.093 g, 0.66 mmol) in DMF (0.5 mL), dropwise, and stirred for 5minutes. The reaction mixture was quenched with ice water (10 mL) andextracted with EtOAc (3×15 mL). The organic layers were combined andwashed with water (3×10 mL) and brine (10 mL), dried over Na₂SO₄, andconcentrated under reduced pressure. The residue was purified by flashchromatography eluting with 1%-8% MeOH/CH₂Cl₂ to afford the titlecompound F32 as a gum (0.065 g, 31%).

The following molecules were made in accordance with the proceduresdisclosed in example 14:

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-2-(1-ethyl-2-oxoazetidin-3-yl)acetamide(Compound F84) was isolated as a gum (0.033 g, 15%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-2-(2-oxo-1-(4-trifluoromethyl)benzyl)azetidin-3-yl)acetamide (Compound F14) was isolated as agum (0.080 g, 27%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-2-(2-oxo-1-((6-trifluoromethyl)pyridin-3-yl)methyl)azetidin-3-yl)acetamide)(Compound F117) was isolated as a gum (0.050 g, 17%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-(1-methyl-2-oxoazetidin-3-yl)propanamide(Compound F119) was isolated as a gum (0.054 g, 25%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-(1-ethyl-2-oxoazetidin-3-yl)propanamide(Compound F103) was isolated as a gum (0.076 g, 34%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-3-1(1-((2,2-difluorocyclopropyl)methyl)-2-oxoazetidin-3-yl)-N-ethylpropanamide (CompoundF74) was isolated as a gum (0.0098 g, 8%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-(2-oxo-1-(4-trifluoromethyl)benzyl)azetidin-3-yl)propanamide (Compound F129) was isolated asa gum (0.166 g, 55%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-(2-oxo-1-((6-(trifluoromethyl)pyridin-3-yl)methyl)azetidin-3-yl)propanamide(Compound F91) was isolated as a gum (0.057 g, 19%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-4-(1-methyl-2-oxoazetidin-3-yl)butanamide(Compound F53) was isolated as a gum (0.112 g, 50%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-4-(1-ethyl-2-oxoazetidin-3-yl)butanamide(Compound F81) was isolated as a gum (0.112 g, 48%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-4-(1-((2,2-difluorocyclopropyl)methyl)-2-oxoazetidin-3-yl)-N-ethylbutanamide(Compound F104) was isolated as a gum (0.010 g, 8%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-4-(2-oxo-1-(4-(trifluoromethyl)benzyl)azetidin-3-yl)butanamide (Compound F127) was isolated as a gum (0.121 g,39%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-4-(2-oxo-1-((6-(trifluoromethyl)pyridin-3-yl)methyl)azetidin-3-yl)butanamide(Compound F87) was isolated as a gum (0.125 g, 40%).

Example 15 Preparation of tert-butyl((1R,4S)-4-((3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(methyl)carbamoyl)cyclopent-2-en-1-yl)carbamate

A solution of 3-chloro-N-methyl-1-(pyridin-3-yl)-1H-pyrazol-4-amine(0.20 g, 0.96 mmol) in THF (10 mL) was cooled to a temperature of about−78° C. LHMDS (1 M solution in hexanes, 1.0 mL, 1.00 mmol) was added,and the solution was stirred at a temperature of about −78° C. for 15minutes. A solution of (1R,4S)-tert-butyl3-oxo-2-azabicyclo[2.2.1]hept-5-ene-2-carboxylate (0.20 g, 0.96 mmol)dissolved in THF (3 mL) was added to the solution at a temperature ofabout −78° C. in one portion. After stirring for one hour at atemperature of about −78° C., the cooling bath was removed and thereaction warmed to a temperature of about 20° C. After stirring for anadditional five minutes, acetic acid (AcOH, 0.1 mL) was added to thesolution. The reaction mixture was concentrated and purified via silicagel chromatography eluting with EtOAc/hexanes to give the title compoundF109 as a white solid (0.25 g, 59%).

The following molecules were made in accordance with the proceduresdisclosed in example 15:

tert-Butyl((1S,4R)-4-((3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(methyl)carbamoyl)cyclopent-2-en-1-yl)carbamate (Compound F116) was isolated asa pink foam (3.46 g, 60%).

Example 16 Preparation(1S,4R)-4-amino-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-methylcyclopent-2-enecarboxamide2,2,2-trifluoroacetate

To a solution of tert-butyl((1R,4S)-4-((3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(methyl)carbamoyl)cyclopent-2-en-1-yl)carbamate(0.13 g, 0.31 mmol) in CH₂Cl₂ (4 mL) was added TFA (4 mL). The reactionwas left to stand for 20 minutes with occasional swirling. The reactionmixture was concentrated in vacuo at a temperature of about 40° C.resulting in the isolation of the title compound C6 as a clear oil (0.13g, 94%): ¹H NMR (400 MHz, CD₃OD) δ 9.02 (dd, J=2.7, 0.7 Hz, 1H), 8.70(s, 1H), 8.54 (dd, J=5.0, 1.4 Hz, 1H), 8.30 (ddd, J=8.4, 2.7, 1.4 Hz,1H), 7.63 (ddd, J=8.4, 5.0, 0.7 Hz, 1H), 6.09 (ddd, J=5.6, 2.7, 1.0 Hz,1H), 5.92 (dt, J=5.6, 2.1 Hz, 1H), 4.16 (d, 7.7 Hz, 1H), 3.80-3.72 (m,1H), 2.98 (s, 3H), 2.29 (dt, J=14.3, 7.9 Hz, 1H), 2.01 (dt, J=14.3, 2.5Hz, 1H); ¹³C NMR (101 MHz, CDCl₃) δ 179.16, 164.09, 163.71, 163.33,162.94, 145.04, 142.05, 141.15, 137.81, 136.71, 134.11, 134.06, 132.73,131.26, 129.77, 123.78, 120.92, 118.06, 115.21, 59.80, 51.85, 40.50,36.87; ESIMS m/z 318 ([M+H]⁺).

Example 17 Preparation of(1S,4R)-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-methyl-4-(2,2,2-trifluoroacetamido)cyclopent-2-enecarboxamide(Compound F126) and(1S,4R)-4-acetamido-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-methyl-cyclopent-2-enecarboxamide(Compound F24)

To a solution of(1S,4R)-4-amino-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-methylcyclopent-2-enecarboxamide2,2,2-trifluoroacetate (0.906 mg, 2.10 mmol) dissolved in CH₂Cl₂ (25 mL)was added triethylamine (0.637 mg, 6.29 mmol) and acetyl chloride (1 Min CH₂Cl₂, 3.15 mL, 3.15 mmol). After stirring for 24 hours, thereaction was diluted with saturated aqueous NaHCO₃ (15 mL) and thephases were separated. The organic layer was dried with anhydrousNa₂SO₄, filtered and concentrated. The resulting residue was purified bysilica gel chromatography eluting first with EtOAC/hexanes providingF126 as a white foam (0.417 g, 48%) followed by eluting with MeOH/CH₂Cl₂to provide compound F24 as a white foam (0.364 g, 48%).

Example 18 Preparation(1R,4S)-4-amino-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-methylcyclopent-2-enecarboxamidedihydrochloride

Solid tert-butyl((1S,4R)-4-((3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(methyl)carbamoyl)cyclopent-2-en-1-yl)carbamate (0.10 g, 0.25 mmol) was combinedwith hydrochloric acid (HCl, 4 M in 1,4-dioxane, 2.0 mL, 8.0 mmol) andMeOH (1 mL). After stirring for 3.5 hours, the reaction mixture wasconcentrated to afford the title compound C7 as a greenish yellow solid(0.095 g, 99%): ¹H NMR (400 MHz, CD₃OD) δ 9.51 (d, J=2.3 Hz, 1H),9.15-9.09 (m, 2H), 8.90 (d, J=5.5 Hz, 1H), 8.30 (dd, J=8.7, 5.6 Hz, 1H),6.26-6.19 (m, 1H), 6.06 (dt, J=5.5, 1.7 Hz, 1H), 4.30 (d, J=7.4 Hz, 1H),3.89 (d, J=7.5 Hz, 1H), 3.30 (s, 3H), 2.43 (dt, J=15.0, 7.7 Hz, 1H),2.13 (dt, J=14.4, 2.5 Hz, 1H); ¹³C NMR (101 MHz, CD₃OD) δ 176.53,142.82, 141.12, 139.99, 138.74, 136.06, 134.13, 131.51, 130.90, 129.52,127.40, 68.16, 57.35, 37.99, 34.44; ESIMS m/z 318 ([M+H]⁺).

Example 19 Preparation of(1R,4S)-4-acetamido-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-methyl-cyclopent-2-enecarboxamide

To a suspension of(1R,4S)-4-amino-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-methylcyclopent-2-enecarboxamidedihydrochloride (0.065 g, 0.17 mmol) in CH₂Cl₂ (2 mL) was addedtriethylamine (0.084 g, 0.83 mmol) followed by acetyl chloride (1 M inCH₂Cl₂, 0.25 mL, 0.25 mmol). After stirring for 24 hours, the reactionproduct was purified by direct application to silica gel chromatographyeluting with MeOH/CH₂Cl₂ to provide the title compound F86 as yellowfoam (0.040 g, 67%).

Example 20 Preparation of(R)-4-acetamido-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-methyl-cyclopent-1-enecarboxamide

To a solution of(1R,4S)-4-acetamido-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-methyl-cyclopent-2-enecarboxamide(0.230 g, 0.639 mmol) dissolved in dimethylsulfoxide (DMSO, 10 mL) wasadded 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, 4.00 mL, 26.7 mmol).After stirring for 4 hours at a temperature of 100° C., the reaction wascooled and diluted with saturated aqueous NH₄Cl (200 mL) and extractedwith EtOAc. The organic layer was dried with anhydrous Na₂SO₄, filteredand concentrated. The resulting residue was purified by silica gelchromatography eluting with MeOH/CH₂Cl₂ to provide the title compoundF41 as a yellow oil (0.120 g, 44%).

Example 21 Preparation of tert-butyl((1S,4R)-4-((3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(methyl)carbamoyl)cyclopentan-1-yl)carbamate

To a solution of 3-chloro-N-methyl-1-(pyridin-3-yl)-1H-pyrazol-4-amine(0.109 g, 0.523 mmol) and(1S,3R)-3-((tert-butoxycarbonyl)amino)cyclopentanecarboxylic acid (0.120g, 0.523 mmol) in DMF (2.09 mL) was addedO-(7-azabenzotriazol-1-yl)-N,N,N′,N′-tetramethyl uroniumhexafluorophosphate (HATU, 0.219 g, 0.576 mmol) to give a brownsolution. To this solution was added 4-methylmorpholine (0.115 mL, 1.05mmol). The reaction was stirred at room temperature overnight. Thematerial was diluted with EtOAc and water. The organic layer was driedwith MgSO4, filtered and concentrated to give orange oil, which waspurified by silica gel chromatography eluting with EtOAc/hexanesprovided the title compound F45 as an orange oil (0.100 g, 39%).

Example 22 Preparation ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-4-oxopentanamide

To a mixture of 3-chloro-N-ethyl-1-(pyridin-3-yl)-1H-pyrazol-4-amine(1.00 g, 4.49 mmol), 4-oxopentanoic acid (0.626 g, 5.39 mmol) and DMAP(0.658 g, 5.39 mmol) in diethyl ether (10 mL) was addedN,N′-methanediylidenebis(propan-2-amine) (0.680 g, 5.39 mmol) at atemperature of about 0° C., and the mixture stirred for 30 minutes. Themixture was warmed to room temperature and stirred at room temperaturefor 1 hour. To the mixture was added another 1.2 eq of diisopropylcarbodiimide (0.820 g, 6.47 mmol) and stirred at room temperature for 16hours. The mixture was quenched with saturated aqueous NH₄Cl and dilutedwith EtOAc. The organic phase was separated, and the aqueous phaseextracted with EtOAc. The combined organic phase was washed with brine,dried over MgSO₄ and filtered. Removal of the volatiles under reducedpressure gave light brown gum, which was purified on silica gel elutingwith MeOH/CH₂Cl₂ to give the title compound C8 as a colorless gum (1.41g, 93%): ¹H NMR (400 MHz, CDCl₃) δ 9.03 (dd, J=4.9, 2.6 Hz, 2H), 8.61(m, 2H), 8.16 (d, J=3.2 Hz, 1H), 8.11 (dddd, J=8.4, 4.1, 2.6, 1.3 Hz,2H), 7.50 (dt, J=8.5, 4.4 Hz, 2H), 3.66 (q, J=7.0 Hz, 2H), 2.76 (t,J=6.2 Hz, 2H), 2.37 (t, J=6.1 Hz, 3H), 1.12 (td, J=7.1, 1.3 Hz, 3H);ESIMS m/z 321 ([M+H]⁺).

Example 23 Preparation of(E/Z)-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-4-(methoxyimino)pentanamide

To a stirred solution ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-4-oxopentanamide(0.142 g, 0.443 mmol) dissolved in a mixture of pyridine (0.44 mL) andethanol (0.44 mL) was added O-methylhydroxylamine hydrochloride (0.129mg, 1.50 mmol). The reaction mixture was heated at a temperature of 60°C. for 16 hours. The reaction mixture was cooled to room temperature,diluted with CH₂Cl₂ and then washed with water. The phases wereseparated, the combined organic layers were dried over MgSO₄, filtered,concentrated and purified by silica gel chromatography eluting with0%-50% acetone/hexanes to afford the title compound F92 as a colorlessoil (0.116 g, 75%).

The following molecules were made in accordance with the proceduresdisclosed in example 23:

(E/Z)-N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-4-(methoxyimino)-N-methylpentanamide(Compound F60) was isolated as a colorless oil (0.188 g, 75%).

(E/Z)-N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-4-(isopropoxyimino)-N-methylpentanamide(Compound F130) was isolated as a colorless oil (0.135 g, 68%).

Example 24 Preparation of3-chloro-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethylpropanamide

To a stirred solution of3-chloro-N-ethyl-1-(pyridin-3-yl)-1H-pyrazol-4-amine dihydrochloride(1.00 g, 3.38 mmol) in CH₂Cl₂ (7 mL) was added propylene oxide (1.00 mL,13.5 mmol) followed by 3-chloropropanoyl chloride (0.360 mL, 3.72 mmol).This was stirred at room temperature for 16 hours, and then the reactionmixture was then diluted with CH₂Cl₂ and washed with water. The phaseswere separated, the organic were dried, concentrated and purified bysilica gel chromatography eluting with 0%-50% acetone/hexanes to afforda white solid (0.850 g, 80%): mp 85-86° C.; ¹H NMR (400 MHz, CDCl₃) δ8.96 (d, J=2.6 Hz, 1H), 8.64 (dd, J=4.7, 1.4 Hz, 1H), 8.05 (ddd, J=8.3,2.7, 1.4 Hz, 1H), 7.98 (s, 1H), 7.47 (ddd, J=8.4, 4.8, 0.6 Hz, 1H), 3.80(t, J=6.7 Hz, 2H), 3.74 (q, J=7.1 Hz, 2H), 2.64 (t, J=6.7 Hz, 2H), 1.18(t, J=7.2 Hz, 3H); ESIMS m/z 313 ([M+H]⁺).

The following molecules were made in accordance with the proceduresdisclosed in example 24:

2-Chloro-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethylpropanamide(Compound C10) was isolated as a white solid (1.25 g, 59%).

2-Chloro-N-[3-chloro-1-(3-pyridyl)pyrazol-4-yl]-N-ethyl-acetamide(Compound CA2) was isolated as an orange oil (0.579 g, 86%): ¹H NMR (400MHz, CDCl₃) δ 9.21 (s, 1H), 8.97 (d, J=2.6 Hz, 1H), 8.70-8.61 (m, 1H),8.07 (s, 1H), 7.53-7.41 (m, 1H), 4.07-3.90 (m, 21H), 3.73 (s, 2H),1.22-1.11 (m, 3H).

Example 25 Preparation ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-(methylamino)propanamide

Monomethylamine (33% solution in EtOH, 11 mL, 90 mmol) and3-chloro-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethylpropanamide(1.9 g, 6.0 mmol) was capped in a 10-20 mL vial and heated on a BIOTAGEINITIATOR® microwave reactor for 1 hour at a temperature of about 100°C. with external IR-sensor temperature monitoring from the side of thevessel. The reaction mixture was then concentrated and purified bysilica gel chromatography eluting with 0%-10% MeOH/CH₂Cl₂ to afford ayellow oil (1.7 g, 93%): IR (KBr thin film) 3055, 2971, 2773, 1656 cm⁻¹;¹H NMR (400 MHz, Acetone-d₆) δ 9.12 (dd, J=6.7, 2.6 Hz, 1H), 8.90 (s,1H), 8.58 (dd, J=4.7, 1.4 Hz, 1H), 8.25 (m, 1H), 7.56 (m, 1H), 3.67 (q,J=7.1 Hz, 2H), 3.01 (t, J=6.5 Hz, 2H), 2.66 (t, J=6.4 Hz, 2H), 2.50 (s,3H), 1.12 (t, J=7.2 Hz, 3H); ESIMS m/z 308 ([M+H]⁺).

Example 26 Preparation ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-(N-methylacetamido)propanamide

To a stirred solution ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-(methylamino)propanamide dihydrochloride (0.060 g, 0.16 mmol) in CH₂Cl₂ (0.5 mL) wasadded DIPEA (0.081 g, 0.60 mmol) followed by acetyl chloride (0.019 mg,0.24 mmol). The reaction mixture was stirred for 16 hours. The reactionmixture was then diluted with CH₂Cl₂ and washed with water. The organicphase was separated, dried, concentrated, and then purified by silicagel chromatography eluting with 0%-10% MeOH/CH₂Cl₂ to afford the titlecompound F64 as a colorless oil (0.025 g, 45%).

The following molecules were made in accordance with the proceduresdisclosed in example 26:

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-(1,3,3-trimethylureido)propanamide(Compound F121) was isolated as a light yellow oil (0.071 g, 66%).

Ethyl(3-((3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)amino)-3-oxopropyl)(methyl)carbamate(Compound F42) was isolated as colorless oil (0.065 g, 71%).

S-Ethyl(3-((3-chloro-1-(pyridin-3yl)-1H-pyrazol-4-yl)(ethyl)amino)-3-oxopropyl)(methyl)carbamothioate (Compound F40) was isolated as a colorless oil (0.065 g,68%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-2-(1,3,3-trimethylureido)propanamide(Compound F114) was isolated as an orange solid (0.147 g, 96%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-2-(N-methylacetamido)propanamide(Compound F96) was isolated as an oil (0.096 g, 68%).

S-Ethyl(1-((3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)amino)-1-oxopropan-2-yl)(methyl)carbamothioate (Compound F79) was isolated as a yellow oil (0.060 g,41%).

N-(1-((3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)amino)-1-oxopropan-2-yl)-3,3,3-trifluoro-N-methylpropanamide(Compound F66) was isolated as a colorless oil (0.096 g, 57%).

Example 27 Preparation of1-((3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)amino)-1-oxopropan-2-ylacetate

To a stirred solution of3-chloro-N-ethyl-1-(pyridin-3-yl)-1H-pyrazol-4-amine dihydrochloride(3.00 g, 10.2 mmol) in CH₂Cl₂ (20 mL) cooled in an ice bath were addedtriethylamine (5.7 mL, 40.6 mmol) followed by dropwise addition1-chloro-1-oxopropan-2-yl acetate (1.3 mL, 10.2 mmol). The reactionmixture was stirred overnight warming to room temperature. The reactionmixture was then diluted with CH₂Cl₂ and washed with water. The phaseswere separated, and the organics were dried over MgSO₄, filtered andconcentrated. The residue was purified by silica gel chromatographyeluting with 0%-70% acetone/hexanes to afford the title compound C12 asa tan taffy-like solid (3.2 g, 93%): ¹H NMR (400 MHz, CDCl₃) δ 8.99 (d,J=2.5 Hz, 1H), 8.62 (dd, J=4.8, 1.3 Hz, 1H), 8.18 (s, 1H), 8.04 (ddd,J=8.3, 2.7, 1.4 Hz, 1H), 7.46 (ddd, J=8.4, 4.8, 0.5 Hz, 1H), 5.01 (d,J=6.5 Hz, 1H), 3.54 (m, 2H), 2.09 (s, 3H), 1.39 (d, J=6.8 Hz, 3H), 1.17(t, J=7.2 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 171.01, 148.62, 140.57,140.24, 135.63, 127.56, 126.33, 124.06, 122.58, 67.49, 43.74, 20.61,16.80, 12.57 (one carbon signal not located); ESIMS m/z 336.4 ([M+H]⁺),335.0 ([M−H]⁻).

Example 28 Preparation ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-2-hydroxypropanamide

To a stirred solution of1-((3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)amino)-1-oxopropan-2-yl acetate (2.4 g, 7.1 mmol) in MeOH (9 mL) and THF(9 mL) was added lithium hydroxide (LiOH, 2 M, 7.0 mL, 14 mmol). Thereaction mixture was stirred for two hours at room temperature, and thenthe reaction mixture pH was made neutral by the addition of aq. 2M HCl.After the mixture was then extracted with EtOAc, the organics phaseswere combined, dried over MgSO₄, filtered and concentrated in vacuo toafford the title compound C13 as a white solid (1.9 g, 88%): mp 137-138°C.; ¹H NMR (400 MHz, DMSO) δ 9.08 (d, J=2.5 Hz, 1H), 8.98 (s, 1H), 8.58(dd, J=4.7, 1.1 Hz, 1H), 8.23 (ddd, J=8.4, 2.6, 1.3 Hz, 1H), 7.59 (dd,J=8.3, 4.7 Hz, 1H), 4.97 (d, J=7.6 Hz, 1H), 4.08 (m, 1H), 3.57 (d,J=50.6 Hz, 2H), 1.10 (d, J=6.5 Hz, 3H), 1.07 (t, J=7.1 Hz, 3H); ESIMSm/z 295.6 ([M+H]⁺).

Example 29 Preparation of1-((3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)amino)-1-oxopropan-2-yldimethylcarbamate

To a stirred solution ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-2-hydroxypropanamide(0.10 g, 0.34 mmol) in CH₂Cl₂ (1.1 mL) was added dimethylcarbamicchloride (0.073 g, 0.68 mmol). The reaction mixture was stirred at roomtemperature for 16 hours, and then diluted with CH₂Cl₂, washed withwater. The phases were separated, dried and concentrated. The residuewas purified by basic alumina gel chromatography eluting with 0%-70%acetone/hexanes to afford the title compound F93 as a light yellow oil(0.11 g, 87%).

The following molecules were made in accordance with the proceduresdisclosed in example 29:

1-((3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)amino)-1-oxopropan-2-ylmethoxy(methyl) carbamate (Compound F16) was isolated as a colorless oil(0.127 g, 82%).

Example 30 Preparation of tert-butyl3-((3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)carbamoyl)pyrrolidine-1-carboxylate

To a stirred solution of3-chloro-N-ethyl-1-(pyridin-3-yl)-1H-pyrazol-4-amine dihydrochloride(0.20 g, 0.68 mmol) in CH₂Cl₂ (1.4 mL) were added DIPEA (0.35 g, 2.7mmol) followed by 1-(tert-butoxycarbonyl)pyrrolidine-3-carboxylic acid(0.22 g, 1.0 mmol) and EDCI (0.20 g, 1.0 mmol). The reaction mixture wasstirred at room temperature for 16 hours, then concentrated. The residuewas purified by silica gel chromatography eluting with 0%-50%acetone/hexanes to afford a colorless oil (0.14 g, 49%).

Example 31 Preparation ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-methyl-3-(2-oxooxazolidin-3-yl)propanamide

To a solution of oxazolidin-2-one (0.038 g, 0.44 mmol) in DMF (3 mL) wasadded NaH (60% dispersion in oil, 0.011 g, 0.44 mmol). The mixture wasstirred at a temperature of about 0° C. for 10 minutes, and3-chloro-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-methylpropanamide (0.12 g, 0.40 mmol) was added. The resulting brown-yellowmixture was stirred at room temperature for two hours and diluted withsaturated aqueous NH₄Cl. The mixture was diluted with EtOAc andsaturated aqueous NaCl solution. The organic phase was separated, andthe aqueous phase extracted with EtOAc (2×50 mL). The combined EtOAcextracts was dried over MgSO₄, filtered, and concentrated under reducedpressure to give light brown gum. The gum was purified on silica geleluting with MeOH/CH₂Cl₂ to give the title compound F31 as a colorlessoil (0.13 g, 94%).

The following molecules were made in accordance with the proceduresdisclosed in example 31:

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-methyl-3-(2-oxothiazolidin-3-yl)propanamide(Compound F38) was isolated as a light brown gum (0.029 g, 19%).

3-(3-Acetyl-1H-pyrazol-1-yl)-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethylpropanamide(Compound FA68) was isolated as a light brown oil (0.221 g, 59% yield).

Example 32 Preparation ofN-(3-((3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)amino)-3-oxopropyl)-N-(2,2-difluoroethyl)-2,2-difluorocyclopropanecarboxamide

To a solution ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-3-((2,2-difluoroethyl)amino)-N-ethylpropanamide (0.10 g, 0.28 mmol) in CH₂Cl₂ (2 mL)were added 2,2-difluoro cyclopropanecarboxylic acid (0.041 g, 0.34mmol), DMAP (0.034 g, 0.28 mmol) andN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-3-((2,2-difluoroethyl)amino)-N-ethylpropanamide(0.10 g, 0.28 mmol), and the mixture stirred at room temperature for 2hours. The mixture was diluted with CH₂Cl₂ and washed with saturatedaqueous NH₄Cl and brine, dried over MgSO₄, and concentrated underreduced pressure to give pink oil. The residue oil was purified onsilica gel eluting with MeOH/CH₂Cl₂ to give the title compound F34 as acolorless oil (0.079 g, 58%).

The following molecules were made in accordance with the proceduresdisclosed in example 32:

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-3-(2-cyclopropyl-N-(2,2-difluoroethyl)acetamido)-N-ethylpropanamide(Compound F125) was isolated as a colorless oil (0.092 g, 75%).

N-(3-((3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)amino)-3-oxopropyl)-N-(2,2-difluoroethyl)-2,2-difluoro-1-methylcyclopropanecarboxamide (Compound F35) was isolated as a light brown oil (0.068 g,51% yield).

N-(3-((3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)amino)-3-oxopropyl)-N-(2,2-difluoroethyl)-4,4,4-trifluorobutanamide(Compound F89) was isolated as a colorless oil (0.079 g, 56%).

Example 33 Preparation ofN-(3-((3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(ethyl)amino)-3-oxopropyl)-N-(2,2-difluoroethyl)-1H-imidazole-1-carboxamide

To a solution ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-3-((2,2-difluoroethyl)amino)-N-ethylpropanamide(0.10 g, 0.28 mmol) in DMF (1 mL) was added carbonyl dimidazole (0.045g, 0.28 mmol), and the mixture stirred at room temperature for 3 hours.To the mixture was added (2,2-difluorocyclopropyl)methanol (0.030 g,0.28 mmol) and stirred at room temperature for 12 hours. The mixture wasdiluted with CH₂Cl₂ and washed with saturated aqueous NH₄Cl and brine,dried over MgSO₄, and concentrated under reduced pressure to give brownoil. The residue oil was purified on silica gel eluting with MeOH/CH₂Cl₂to give the title compound F17 as a colorless gum (0.069 g, 55%).

Example 34 Preparation of(E)-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-4-(hydroxyimino)pentanamide

To a solution ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-4-oxo pentanamide(0.10 g, 0.31 mmol) in THF (3.0 mL) was added a solution of sodiumacetate (0.064 g, 0.78 mmol) and hydroxylamine.HCl salt (0.033 g, 0.47mmol) in water (0.5 mL), and the mixture stirred for one hour. Themixture was diluted with EtOAc and water. The organic phase wasseparated, and the aqueous extracted with EtOAc. The combined organicphase was washed with brine, dried over MgSO₄, and filtered. Removal ofthe volatiles under reduced pressure gave colorless gum, which waspurified on silica gel eluting with MeOH/CH₂Cl₂ to give the titlecompound F105 as a colorless gum (0.088 g, 80%).

The following molecules were made in accordance with the proceduresdisclosed in example 34:

(E/Z)-N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-(3-(1-(methoxyimino)ethyl)-1H-pyrazol-1-yl)propanamide(Compound FA1) was isolated as a light yellow oil (0.043 g, 80%).

(E/Z)-N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-(3-(1-(isopropoxyimino)ethyl)-1H-pyrazol-1-yl)propanamide(Compound FA2) was isolated as a colorless gum (0.048 g, 84%).

(Z)-N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-4-(hydroxyimino)pentanamide(Compound FA46) was isolated as a colorless oil (0.158 g, 62%).

(E)-N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-4-(hydroxyimino)pentanamide(Compound FA47) was isolated as a colorless oil (0.065 g, 26%).

(E)-N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-4-(hydroxyimino)-2-methylpentanamide(Compound FA52) was isolated as a colorless oil (0.015 g, 16%).

(Z)-N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-4-(hydroxyimino)-2-methylpentanamide(Compound FA53) was isolated as a colorless oil (0.051 g, 54%).

(Z)-N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-4-(hydroxyimino)-2-methylbutanamide(Compound FA54) was isolated as a colorless oil (0.098 g, 17%).

(E)-N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-4-(hydroxyimino)-2-methylbutanamide(Compound FA55) was isolated as a colorless oil (0.148 g, 26%).

(E/Z)-N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-4-(hydroxyimino)butanamide(Compound FA56) was isolated as a colorless oil (0.204 g, 68%).

Example 35 Preparation of(E/Z)-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-4-(((2,2-difluorocyclopropyl)methoxy)imino)-N-ethylpentanamide

To a solution of(E/Z)-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-4-(hydroxyimino)pentanamide (0.10 g, 0.30 mmol) in dry THF (1 mL) at a temperature ofabout 0° C. under N₂ was added NaH (60% dispersion in oil, 0.013 g, 0.31mmol) followed by 2-(bromomethyl)-1,1-difluorocyclopropane (0.056 g,0.33 mmol). The mixture was stirred for one hour and warmed to roomtemperature. After stirring for additional one hour, the mixture wasquenched with saturated aqueous NH₄Cl and diluted with EtOAc. Theorganic phase was separated, and the aqueous phase extracted with EtOAc.The combined organic phase was washed with brine, dried over MgSO₄, andfiltered. Removal of the volatiles under reduced pressure gave colorlessgum, which was purified on silica gel eluting with MeOH/CH₂Cl₂ to givethe title compound F72 as a brown oil (0.062 g, 46%).

The following molecules were made in accordance with the proceduresdisclosed in example 35:

(E/Z)-N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-4-((2,2,2-trifluoroethoxy)imino)pentanamide (Compound F51) was isolated as a colorless oil (0.071 g,54%).

(E/Z)-N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-4-((2-(2,2-difluorocyclopropyl)ethoxy)imino)-N-ethylpentanamide (Compound F20) was isolatedas a colorless oil (0.059 g, 43%).

(E/Z)-N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-4-(((6-(trifluoromethyl)pyridin-2-yl)oxy)imino)pentanamide(Compound F59) was isolated as a colorless oil (0.095 g, 75%).

(E/Z)-N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-4-(((4-(trifluoromethyl)pyridin-2-yl)oxy)imino)pentanamide(Compound F36) was isolated as a colorless oil (0.095 g, 82%).

(E/Z)-N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-4-(((5,5,5-trifluoropentyl)oxy)imino)pentanamide (Compound FA4) was isolated as a colorless gum (0.071g, 52%).

(E/Z)-N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-4-((4,4,4-trifluorobutoxy)imino)pentanamide (Compound FA19) was isolated as a light yellow gum (0.098 g,74%).

(E/Z)-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-4-((4-fluorobutoxy)imino)pentanamide(Compound FA20) was isolated as a light yellow gum (0.063 g, 73%).

(E/Z)-N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-4-(((3,3-difluorocyclobutyl)methoxy)imino)-N-ethylpentanamide(Compound FA21) was isolated as colorless gum (0.045 g, 34%).

(E/Z)-N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-4-(((6-(trifluoromethyl)pyridin-3-yl)methoxy)imino)pentanamide(Compound FA22) was isolated as a light brown gum (0.135 g, 87%).

(E/Z)-4-(((5-(tert-Butyl)-1,2,4-oxadiazol-3-yl)methoxy)imino)-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethylpentanamide(Compound FA23) was isolated as a light brown gum (0.124 g, 83%).

(E/Z)-N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-4-(((3-chloro-5-(trifluoromethyl)pyridin-2-yl)methoxy)imino)-N-ethylpentanamide(Compound FA24) was isolated a light brown gum (0.102 g, 61%).

(E/Z)-N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-4-(((3,5-dimethylisoxazol-4-yl)methoxy)imino)-N-ethylpentanamide(Compound FA25) was isolated as a light brown gum (0.099 g, 71%).

(E)-N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-4-(thiophen-2-yl)-4-((4,4,4-trifluorobutoxy)imino)butanamide (Compound FA26) was isolated as light yellow gum (0.051g, 38%).

(Z)-N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-4-(thiophen-2-yl)-4-((4,4,4-trifluorobutoxy)imino)butanamide (Compound FA27) was isolated as a light yellow gum(0.018 g, 13%).

(E)-N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-4-(thiophen-2-yl)-4-(((5,5,5-trifluoropentyl)oxy)imino)butanamide(Compound FA28) was isolated as a light brown gum (0.055 g, 40%).

(Z)-N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-4-(thiophen-2-yl)-4-(((5,5,5-trifluoropentyl)oxy)imino)butanamide(Compound FA29) was isolated as a light brown gum (0.021 g, 14%).

(E)-N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-4-(((3,3-difluorocyclobutyl)methoxy)imino)-N-ethyl-4-(thiophen-2-yl)butanamide (CompoundFA30) was isolated as a light brown gum (0.053 g, 42%).

(Z)-N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-4-(((3,3-difluorocyclobutyl)methoxy)imino)-N-ethyl-4-(thiophen-2-yl)butanamide (CompoundFA31) was isolated as a light brown gum (0.022 g, 17%).

(E/Z)-N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-4-(thiophen-2-yl)-4-((2,2,2-trifluoroethoxy)imino)butanamide(Compound FA35) was isolated as a light brown gum (0.088 g, 69%).

(E)-N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-4-(thiophen-2-yl)-4-(((6-(trifluoromethyl)pyridin-3-yl)methoxy)imino)butanamide (Compound FA36) was isolated as alight brown gum (0.058 g, 39%).

(Z)-N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-4-(thiophen-2-yl)-4-(((6-(trifluoromethyl)pyridin-3-yl)methoxy)imino)butanamide (Compound FA37) was isolated aslight brown gum (0.030 g, 20%).

(E)-N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-4-(((2,2-difluorocyclopropyl)methoxy)imino)-N-ethyl-4-(thiophen-2-yl)butanamide(Compound FA38) was isolated as a light brown gum (0.040 g, 31%).

(Z)-N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-4-(((2,2-difluorocyclopropyl)methoxy)imino)-N-ethyl-4-(thiophen-2-yl)butanamide(Compound FA39) was isolated as a light brown gum (0.018 g, 14%).

(E/Z)-N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-4-(((4-(trifluoromethoxy)benzyl)oxy)imino)pentanamide (Compound FA40) was isolated as a light brown gum(0.044 g, 27%).

(Z)-N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-4-((2-(2,2-difluorocyclopropyl)ethoxy)imino)-N-ethylpentanamide (Compound FA49) wasisolated as a colorless oil (0.55 g, 56%).

(E)-N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-4-((2-(2,2-difluorocyclopropyl)ethoxy)imino)-N-ethylpentanamide (Compound FA50) wasisolated as a colorless oil (0.57 g, 67%).

(Z)-N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-4-((2-(2,2-difluorocyclopropyl)ethoxy)imino)-N-ethyl-2-methylpentanamide (Compound FA57)was isolated as a colorless oil (0.026 g, 41%).

(E)-N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-4-((2-(2,2-difluorocyclopropyl)ethoxy)imino)-N-ethyl-2-methylpentanamide (Compound FA58)was isolated as a colorless oil (0.011 g, 57%).

(Z)-N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-4-((2-(2,2-difluorocyclopropyl)ethoxy)imino)-N-ethyl-2-methylbutanamide (Compound FA59) was isolated asa colorless oil (0.096 g, 47%).

(E)-N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-4-((2-(2,2-difluorocyclopropyl)ethoxy)imino)-N-ethyl-2-methylbutanamide(Compound FA60) was isolated as a colorless oil (0.059 g, 47%).

(E/Z)-N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-4-((2-(2,2-difluorocyclopropyl)ethoxy)imino)-N-ethylbutanamide(Compound FA61) was isolated as a colorless oil (0.208 g, 79%).

Example 36 Preparation ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-3-((2,2-difluoroethyl)amino)-N-ethylpropanamide

To a solution of3-chloro-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethylpropanamide (1.30 g, 4.15 mmol) in 1,4-dioxane (15 mL) were added DIPEA(1.13 g, 8.72 mmol) and 2,2-difluoroethanamine (0.67 g, 8.30 mmol) wascapped in a 10-20 mL vial and heated on a BIOTAGE INITIATOR® microwavereactor for 16 hours at a temperature of 140° C. with external IR-sensortemperature monitoring from the side of the vessel. The mixture wasfiltered, and the solids were washed with EtOAc. The filtrate wasconcentrated under reduced pressure to give brown gum, which waspurified on silica gel eluting MeOH/CH₂Cl₂ to give the title compoundC14 as a brown gum (1.22 g, 73.9%).

Example PE1 Preparation ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-2-(2-oxo-3-(3,3,3-trifluoropropyl)pyrrolidin-1-yl)acetamide

To 3-(3,3,3-trifluoropropyl)pyrrolidin-2-one in an appropriate reactionvessel may be added NaH (from about 1.0 eq to about 2.0 equivalent) in asolvent, such as THF (at a concentration between about 0.01 M to about 1M) followed by2-chloro-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethylacetamide(from about 0.5 eq to about 1.5 eq). The reaction may be stirred at atemperature from about 0° C. to about 25° C. until determined to becomplete. After completion of the reaction, the product may be obtainedusing standard organic chemistry techniques for workup and purification.

The following compounds in Table 5 may be prepared according to theprocedures disclosed in example PE1: P1, P2, P3, P4, P5, P6, P7.

Example PE2 Preparation ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-2-(2-oxo-1-(3,3,3-trifluoropropyl)pyrrolidin-3-yl)acetamide

ToN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-2-(2-oxopyrrolidin-3-yl)acetamidein an appropriate reaction vessel may be added NaH (from about 1.0 eq toabout 2.0 equivalent) in a solvent, such as THF (at a concentrationbetween about 0.01 M to about 1 M) followed by2-chloro-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethylacetamide(from about 1.0 eq to about 2.0 eq). The reaction may be stirred at atemperature from about 0° C. to about 25° C. until determined to becomplete. After completion of the reaction, the product may be obtainedusing standard organic chemistry techniques for workup and purification.

The following compounds in Table 5 may be prepared according to theprocedures disclosed in example PE2: P8, P9, P10, P11, P12, P13, P14,P15, P18, P19.

Example PE3 Preparation ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-1-(3,3,3-trifluoropropanoyl)piperidine-4-carboxamide

In an appropriate reaction vessel, toN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethylpiperidine-4-carboxamidemay be added 3,3,3-trifluoropropanoic acid (about 1.0 to about 2.0 eq),DMAP (about 2.0 to about 3.0 eq), and EDCI (about 1.5 to about 3.0 eq)in a solvent, such as CH₂Cl₂ (at a concentration between about 0.01 M toabout 1 M). The reaction may be stirred at a temperature from about 0°C. to about 50° C. until determined to be completed. After completion ofthe reaction, the product may be obtained using standard organicchemistry techniques for workup and purification.

The following compounds in Table 5 may be prepared according to theprocedures disclosed in example PE3:

P16, P17, P20, P21, P22, P23, P24, P25, P28, P29, P30, P31, P32, P33.

Example PE4 Preparation of(E/Z)-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-7,7,7-trifluoro-3-(methoxyimino)heptanamide

In an appropriate reaction vessel, toN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-7,7,7-trifluoro-3-oxoheptanamidemay be added a solvent system, such as pyridine and ethanol (at aconcentration between about 0.01 M to about 1 M) and O-methylhydroxylamine.hydrochloride (about 2.0 to about 3.0 eq). The reactionmay be stirred at a temperature from about 25° C. to about 80° C. untildetermined to be completed. Following completion of the reaction, theproduct may be obtained using standard organic chemistry techniques forworkup and purification.

The following compounds in Table 5 may be prepared according to theprocedures disclosed in example PE4: P26, P27.

Example PE5 Preparation of(1S,3R)-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-(N-methylacetamido)cyclopentanecarboxamide

In an appropriate reaction vessel, to(1S,3R)-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-(methylamino)cyclopentanecarboxamidemay be added acetyl chloride (about 1.0 to about 2.0 eq) and DMAP (about2.0 to about 3.0 eq) in a solvent, such as CH₂Cl₂ (at a concentrationbetween about 0.01 M to about 1 M). The reaction may be stirred at atemperature from about 0° C. to about 50° C. until determined to becompleted. Following completion of the reaction, the product may beobtained using standard organic chemistry techniques for workup andpurification.

The following compounds in Table 5 may be prepared according to theprocedures disclosed in example PE5: P34, P35, P36, P37.

Example PE6 Preparation ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-1-(3,3,3-trifluoropropanoyl)piperidine-4-carboxamide

In an appropriate reaction vessel, to(1S,3R)-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-(methylamino)cyclopentanecarboxamidemay be added trifluoroacetic anhydride (about 1.0 to about 2.0 eq) andN-methylmorpholine (about 2.0 to about 3.0 eq) in a solvent, such asCH₂Cl₂ (at a concentration between about 0.01 M to about 1 M). Thereaction may be stirred at a temperature from about 0° C. to about 50°C. until determined to be completed. Following completion of thereaction, the product may be obtained using standard organic chemistrytechniques for workup and purification.

The following compounds in Table 5 may be prepared according to theprocedures disclosed in example PE6: P38, P39.

Example 37 Preparation ofN-[3-chloro-1-(3-pyridyl)pyrazol-4-yl]-N-ethyl-3-[2-oxo-1-(2,2,2-trifluoroethyl)pyrrolidin-3-yl]propanamide

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-(2-oxopyrrolidin-3-yl)propanamide(0.037 g, 0.10 mmol) was added to a vial with stir bar, followed sodiumhydride (60% in mineral oil, 0.010 g, 0.26 mmol). The vial was placedunder N2 and chilled to 0° C. THF (1 mL) was then added and the reactionwas allowed to stir for 30 minutes 2,2,2-Trifluoroethyltrifluoromethanesulfonate (0.037 mL, 0.26 mmol) was added neat,dropwise. The reaction stirred overnight. The reaction was adsorbed ontoCELITE®. Purification by flash column chromatography using MeOH/CH₂Cl₂as eluent provided the title compound as a colorless oil (0.011 g, 24%).

The following molecules were made in accordance with the proceduresdisclosed in example 37:

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-3-(1-(2-(2,2-difluorocyclopropyl)ethyl)-2-oxopyrrolidin-3-yl)-N-ethylpropanamide(Compound FA62) was isolated as a colorless oil (0.026 g, 40%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-2-(1-(2-(2,2-difluorocyclopropyl)ethyl)-2-oxopyrrolidin-3-yl)-N-ethylacetamide(Compound FA64) was isolated as a colorless oil (0.027 g, 35%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-2-(2-oxo-1-(2,2,2-trifluoroethyl)pyrrolidin-3-yl)acetamide(Compound FA65) was isolated as a colorless oil (0.047 g, 63%).

Example 38 Preparation ofN-[3-chloro-1-(3-pyridyl)pyrazol-4-yl]-N-ethyl-2-methyl-4-oxo-butanamide

ToN-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-2-methylpent-4-enamide(0.450 g, 1.41 mmol) in a flask with a stir bar dissolved in CH₂Cl₂ (13mL) and MeOH (1.3 mL) was added Sudan III indicator solution (0.01 M,0.060 mL). The flask was attached to an ozone generator and a flow ofoxygen was initiated, with stirring. The reaction was cooled to −78° C.,and the ozone production was bubbled through the solution forapproximately 6 minutes before the pink color was absent and the yellowsolution started to turn green/blue. The ozone generation was arrested,and pure oxygen was bubbled through the reaction for approximately 5minutes as the dark colors faded and the yellow color became prominent.While still at −78° C., triphenylphosphine (0.555 g, 2.12 mmol) wasadded as a solid, and the cooling bath was removed. A nitrogen gas inletwas attached to the flask, and the reaction was allowed to warm slowlyto room temperature. The product was then concentrated and loaded ontoCELITE®. Purification by flash column chromatography using 0-40%acetone/hexanes provided the title compound as a clear yellow oil thatcrystallized upon standing (0.390 g, 73%).

Example 39 Preparation ofN-[3-chloro-1-(3-pyridyl)pyrazol-4-yl]-N-ethyl-2-methyl-4-oxo-pentanamide

N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-2-methyl-4-oxobutanamide(0.390 g, 1.22 mmol) was dissolved in THF (12 mL) at −78° C. To thisstirring solution was added dropwise methylmagnesium bromide (0.446 mL,1.34 mmol). The reaction mixture was stirred at −78° C. for 30 minutesand was warmed to 0° C., at which point the reaction was quenched with asaturated aqueous NH₄Cl solution. The reaction product was extractedwith diethyl ether, and the combined organics were washed with brine,then dried over Na₂SO₄ and concentrated under vacuum to provide a yellowoil. The oil was loaded onto CELITE® and purified by flash columnchromatography using 0-50% acetone/hexanes as eluent. The secondaryalcohol recovered as an impure oil was used immediately. The residualoil was taken up in CH₂Cl₂ (10 mL) and buffered with NaHCO₃ (0.153 g,1.82 mmol). The resulting mixture was cooled to 0° C. and Dess-Martinperiodinane (0.516 g, 1.22 mmol) was added in a single portion. Thereaction mixture was stirred at 0° C. for 1 hour, then was warmed toroom temperature. The reaction was quenched by slow addition of asaturated aqueous sodium bisulfite solution, and extracted with CH₂Cl₂.The organic layer was washed with brine, dried over Na₂SO₄ andconcentrated to an oil that was loaded directly onto CELITE®.Purification by flash column chromatography using 0-40% acetone/hexanesas eluent provided the title compound as a clear, colorless oil. (0.0900g, 20% over two steps).

Example 40 Preparation ofN-[3-chloro-1-(3-pyridyl)pyrazol-4-yl]-N-ethyl-2-(2-oxopyrrolidin-3-yl)acetamide

DIPEA (0.629 mL, 4.41 mmol) was dissolved in THF (20 mL) and cooled toabout −78° C. n-Butylithium (1.77 mL, 4.41 mmol) was then added, and thereaction mixture was warmed to about 0° C. for 10 minutes, thenre-cooled to about −78° C. Then,1-(tert-butyldimethylsilyl)pyrrolidin-2-one (0.800 g, 4.01 mmol) wasadded, and the reaction mixture was warmed to 23° C. and stirred for 1hour. The reaction was then re-chilled to −78° C., and2-chloro-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethylacetamide(0.600 g, 2.01 mmol) was then added dropwise as a solution in THF (3mL). The reaction mixture was stirred cold for 30 minutes, then wasallowed to slowly warm to room temperature. After 1 hour, the reactionwas quenched with a NH₄Cl solution and extracted with diethyl ether. Theorganics were washed with brine, dried over Na₂SO₄, and concentrated.The resulting oil was purified by flash column chromatography using0-40% acetone/hexanes as eluent provided the intermediate2-(1-(tert-butyldimethylsilyl)-2-oxopyrrolidin-3-yl)-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethylacetamide(0.604 g, 1.31 mmol). ¹H NMR analysis indicated a mixture of moleculespresent favoring the desired product of about 5:1 over main byproduct.The mixture carried through to the deprotection step without furtherpurification.2-(1-(tert-Butyldimethylsilyl)-2-oxopyrrolidin-3-yl)-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethylacetamide(0.604 g, 1.31 mmol) was dissolved in THF (13 mL) and added wastetrabutylammonium fluoride (TBAF, 1.96 mL, 1.96 mmol). The reactionmixture was stirred for 30 minutes. The reaction product wasconcentrated onto CELITE® and purified by flash column chromatographyusing 40-100% acetone/hexanes as eluent providing the title compound(0.204 g, 30% over 2 steps).

Example 41 Preparation of 3-(but-3-en-1-yl)pyrrolidin-2-one

DIPEA (0.393 mL, 2.76 mmol) was dissolved in THF (25 mL) and chilled to−78° C. n-Butyllithium (1.10 mL, 2.76 mmol) was then added, and thereaction was warmed to 0° C. and re-chilled to −78° C.1-(tert-Butyldimethylsilyl)pyrrolidin-2-one (0.500 g, 2.51 mmol) wasthen added as a solution in THF (1 mL), and the reaction mixture waswarmed to room temperature for 1 hour. The reaction was then re-cooledto −78° C., and 4-bromobut-1-ene (0.305 mL, 3.01 mmol) was addeddropwise in THF (1 mL). The reaction mixture was slowly warmed to roomtemperature overnight. The reaction was concentrated to an oil andloaded onto CELITE®. Purification by flash column chromatography using0-30% acetone/hexanes provided the title compound (0.218 g, 62%): ¹H NMR(400 MHz, CDCl₃) δ 6.15 (s, 1H), 5.82 (ddt, J=17.0, 10.2, 6.6 Hz, 1H),5.09-4.87 (m, 2H), 3.42-3.24 (m, 2H), 2.44-2.25 (m, 2H), 2.24-2.05 (m,2H), 1.99 (dddd, J=13.6, 9.4, 6.9, 4.1 Hz, 1H), 1.78 (dq, J=12.1, 8.4Hz, 1H), 1.45 (dtd, J=13.7, 9.1, 5.5 Hz, 1H); ¹³C NMR (101 MHz, CDCl₃) δ180.44, 137.92, 115.13, 40.29, 40.16, 31.45, 30.05, 27.60; ESIMS m/z 138([M−H]⁻).

Example 42 Preparation of3-(3-but-3-enyl-2-oxo-pyrrolidin-1-yl)-N-[3-chloro-1-(3-pyridyl)pyrazol-4-yl]-N-ethyl-propanamide

To 3-chloro-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethylpropanamide (0.500 g, 1.60 mmol) in acetone (8 mL) was added sodium iodide(0.359 g, 2.40 mmol). The reaction was heated to reflux for 24 hours.The reaction product was filtered and concentrated to provideN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-iodopropanamide(0.363 g, 0.898 mmol), which was used immediately without furtherpurification. To 3-(but-3-en-1-yl)pyrrolidin-2-one (0.125 g, 0.898 mmol)dissolved in DMF (4.49 ml) was added sodium hydride (60% in mineral oil,0.0360 g, 0.898 mmol). The reaction stirred for 45 minutes. Then,N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-iodopropanamide(0.363 g, 0.898 mmol) was added as a solution in DMF (2 mL). Thereaction mixture was allowed to stir at room temperature overnight. Thereaction product was poured into water, extracted with diethyl ether,and washed with brine. The organics were dried and concentrated to givean oil that was purified by flash column chromatography using 0-60%acetone/hexanes as eluent providing the title compound as a clear,colorless oil. (0.257 g, 69%).

Table 3, Table 4, and Table 5 show non-limiting examples of thecompounds of formula I.

Compounds F1, F5, F9, F12, F28, F44, F46, F56, F65, F65, F75, F94, F97,F99, F101, F112, F113, P16, P21, P24, FA5, FA6, FA7, FA8, FA9, FA10,FA11, FA12, FA14, FA15, FA16, FA17, FA41, FA42, FA43, FA44, FA45, andFA66 were prepared according to example 7.

Compounds F2, F19, and F83 were prepared according of example 5.

Compounds F3, F4, F6, F7, F8, F10, F18, F21, F22, F23, F26, F27, F29,F33, F37, F39, F47, F48, F49, F52, F61, F69, F76, F77, F82, F88, F90,F95, F98, F100, F106, F107, F110, F111, F122, F123, F124, P20, P23, FA3,FA13, FA18, FA32, FA33, FA34, FA69, FA70, FA71, and FA76 were preparedaccording to example 1.

Compound F11 was prepared according to example 30.

Compounds F13, F15, F30, F43, F54, F55, F67, F68, F70, F73, F78, F80,F85, F108, F115, F118, and FA77 were prepared according of example 4.

Compounds F14, F32, F53, F74, F81, F84, F87, F91, F103, F104, F117,F119, F127, and F129 were prepared according of example 14.

Compounds F16 and F93 were prepared according of example 29.

Compound F17 was prepared according to example 33.

Compounds F20, F36, F51, F59, F72, FA4, FA19, FA20, FA21, FA22, FA23,FA24, FA25, FA26, FA27, FA28, FA29, FA30, FA31, FA35, FA36, FA37, FA38,FA39, FA40, FA49, FA50, FA57, FA58, FA59, FA60, and FA61 were preparedaccording of example 35.

Compounds F24 and F126 were prepared according of example 17.

Compounds F25, F62, and FA75 were prepared according of example 2.

Compounds F31, F38, and FA68 were prepared according of example 31.

Compounds F34, F35, F89, and F125 were prepared according of example 32.

Compounds F40, F42, F64, F66, F79, F96, F114, and F121 were preparedaccording of example 26.

Compound F41 was prepared according to example 20.

Compound F45 was prepared according to example 21.

Compounds F50, F58, and F71 were prepared according of example 13.

Compound F52 was prepared according to example 11.

Compounds F57, F63, F102, F120, FA72, FA73, and FA74 were preparedaccording of example 8.

Compounds F60, F92, and F130 were prepared according of example 23.

Compound F86 was prepared according to example 19.

Compounds F105, FA1, FA2, FA46, FA47, FA52, FA53, FA54, FA55, and FA56were prepared according to example 34.

Compounds F109 and F116 were prepared according of example 15.

Compound F128 was prepared according to example 9.

Compound F131 was prepared according to example 10.

Compounds P1, FA62, FA64, and FA65 were prepared according to example37.

Compound FA48 was prepared according to example 38.

Compound FA51 was prepared according to example 39.

Compound FA40 was prepared according to example 40.

Compound FA67 was prepared according to example 42.

While the present disclosure may be susceptible to various modificationsand alternative forms, specific embodiments have been described by wayof example in detail herein. However, it should be understood that thepresent disclosure is not intended to be limited to the particular formsdisclosed. Rather, the present disclosure is to cover all modifications,equivalents, and alternatives falling within the scope of the presentdisclosure as defined by the following appended claims and their legalequivalents.

TABLE 3 Appearance, Mass ¹³C NMR, No. Formula Melting Point (m/z) ¹H NMR¹⁹F NMR, IR F1

White Solid HRMS-ESI [M + H]⁺ calcd for C₁₇H₁₉ClF₂N₅O₂, 398.1190; found,398.1209 (400 MHz, CDCl₃) δ 9.00- 8.91 (m, 1H), 8.65 (dd, J = 4.8, 1.4Hz, 1H), 8.05 (ddd, J = 8.3, 2.7, 1.5 Hz, 1H), 7.99 (s, 1H), 7.48 (ddd,J = 8.4, 4.8, 0.8 Hz, 1H), 6.76 (s, 1H), 3.87 (d, J = 4.1 Hz, 2H), 3.75(q, J = 7.2 Hz, 2H), 2.15 (ddd, J = 13.4, 7.9, 6.1 Hz, 1H), 1.51 (t, J =2.3 Hz, 3H), 1.27 (ddd, J = 11.7, 7.8, 4.9 Hz, 1H), 1.20 (t, J = 7.2 Hz,3H) ¹⁹F NMR (376 MHz, CDCl₃) δ −135.58 (d, J = 153.6 Hz), −136.56 (d, J= 153.5 Hz) IR (thin film) 3336, 3093, 1656 cm⁻¹ F2

Pink Solid HRMS-ESI [M + H]⁺ calcd for C₁₇H₂₃ClN₅O₃, 380.1484; found,380.1494 (400 MHz, CDCl₃) δ 8.93 (dd, J = 2.7, 0.7 Hz, 1H), 8.64 (dd, J= 4.7, 1.4 Hz, 1H), 8.03 (ddd, J = 8.3, 2.8, 1.5 Hz, 1H), 7.98 (s, 1H),7.46 (ddd, J = 8.3, 4.8, 0.8 Hz, 1H), 5.37 (br s, 1H), 3.81-3.67(multiple peaks, 4H), 1.42 (s, 9H), 1.17 (t, IR (thin film) 3341, 3094,1675 cm⁻¹ J = 7.2 Hz, 3H) F3

White Semi- Solid ESIMS 344.1 ([M + H]⁺) (400 MHz, CDCl₃) δ 9.07 (s,1H), 8.64 (d, J = 4.8 Hz, 1H), 8.43 (s, 1H), 8.12 (ddd, J = 8.3, 2.6,1.3 Hz, 1H), 7.51 (dd, J = 8.3, 4.8 Hz, 1H), 7.38 (ddd, J = 9.0, 6.6,2.1 Hz, 1H), 7.31 (ddd, J = 6.7, 2.1, 0.7 Hz, 1H), 6.54 (dt, J = 9.0,0.9 Hz, 1H), 6.23 (td, J = 6.7, 1.3 Hz, 1H), 4.54 (s, 2H), 3.29 IR (thinfilm) 1658 cm⁻¹ (s, 3H) F4

Yellow Solid HRMS-ESI [M + H]⁺ calcd for C₁₈H₂₅ClN₅O₃, 394.1640; found,394.1646 ¹H NMR (400 MHz, CDCl₃) δ 8.95 (d, J = 2.8 Hz, 1H), 8.63 (t, J= 5.4 Hz, 1H), 8.11-7.87 (multiple peaks, 2H), 7.45 (dd, J = 8.4, 4.8Hz, 1H), 3.81 (d, J = 27.7 Hz, 2H), 3.71 (q, J = 7.1 Hz, 2H), 2.91 (d, J= 9.9 Hz, 3H), 1.44 (s, 9H), 1.26-1.01 IR (thin film) 3528, 3092, 1687cm⁻¹ (m, 3H) F5

Light Yellow Foam HRMS-ESI [M + H]⁺ calcd for C₁₇H₂₀ClF₃N₅O₂, 418.1252;found, 418.126 (400 MHz, CDCl₃) δ 8.97 (d, J = 2.7 Hz, 1H), 8.69- 8.59(m, 1H), 8.10 (s, 1H), 8.06-7.98 (m, 1H), 7.52- 7.42 (m, 1H), 3.96 (brs, 2H), 3.73 (dq, J = 14.4, 7.2 Hz, 2H), 3.11 (s, 2.6H, major), 2.96 (s,0.4H, minor), 2.68-2.57 (m, 2H), 2.56-2.36 (m, 2H), 1.18 (dt, J = 12.7,7.2 Hz, 3H) ¹⁹F NMR (376 MHz, CDCl₃) δ −66.58 (minor rotamer), −66.65(major rotamer) IR (thin film) 3515, 3093, 1679, 1652 cm⁻¹ F6

White Solid, 102-104° C. ESIMS 334.7 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.97(d, J = 2.7 Hz, 1H), 8.63 (dd, J = 4.7, 1.4 Hz, 1H), 8.13 (s, 1H), 8.02(ddd, J = 8.3, 2.7, 1.4 Hz, 1H), 7.45 (dd, J = 8.4, 4.7 Hz, 1H), 3.94(s, 2H), 3.54 (t, J = 7.1 Hz, 2H), 3.25 (s, 3H), 2.38 (t, J = 8.1 Hz,2H), 2.13-2.04 (m, 2H) IR (thin film) 1666 cm⁻¹ F7

White Solid 154-156° C. ESIMS 352.0 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.97(d, J = 2.6 Hz, 1H), 8.63 (dd, J = 4.8, 1.3 Hz, 1H), 8.11 (s, 1H), 8.01(ddd, J = 8.3, 2.7, 1.4 Hz, 1H), 7.46 (dd, J = 8.3, 4.8 Hz, 1H), 3.96(s, 2H), 3.81 (t, J = 7.3 Hz, 2H), 3.32 (t, J = 7.3 Hz, 2H), 3.25 (s,3H) IR (thin film) 1686, 1650 cm⁻¹ F8

White Solid 114-117° C. ESIMS 376.2 ([M + H]⁺) (400 MHz, CDCl₃) δ 9.00(d, J = 2.6 Hz, 1H), 8.61 (dd, J = 4.7, 1.4 Hz, 1H), 8.12 (s, 1H), 8.06(ddd, J = 8.3, 2.7, 1.5 Hz, 1H), 7.45 (ddd, J = 8.4, 4.8, 0.5 Hz, 1H),3.68 (q, J = 7.0 Hz, 2H), 3.59 (t, J = 7.1 Hz, 2H), 3.36 (t, J = 5.5 Hz,2H), 2.46 (t, J = 7.1 Hz, 2H), 2.31 (t, J = 6.2 Hz, 2H), 1.84-1.68 (m,4H), 1.14 (t, J = 7.2 Hz, 3H) F9

Yellow Oil ESIMS 376 ([M + H]⁺) (400 MHz, CDCl₃) δ 9.02 (dd, J = 2.7,0.8 Hz, 1H), 8.61 (dd, J = 4.8, 1.5 Hz, 1H), 8.17 (s, 1H), 8.07 (ddd, J= 8.4, 2.7, 1.5 Hz, 1H), 7.45 (ddd, J = 8.4, 4.8, 0.8 Hz, 1H), 3.67 (q,J = 7.1 Hz, 2H), 3.64-3.55 (m, 2H), 2.73 (tt, J = 7.0, 4.0 Hz, 1H),2.50-2.36 (m, 2H), 2.15 (s, 3H), 1.14 (t, J = 7.2 Hz, 3H), ¹³C NMR (101MHz, CDCl₃) δ 173.8, 171.3, 148.4, 140.6, 140.2, 135.7, 127.1, 126.3124.0, 123.8, 43.8, 43.2, 32.7, 30.8, 22.7, 13.0, 0.96-0.84 (m, 2H),0.79- 9.3 (2C) 0.68 (m, 2H) F10

White Solid 131-132° C. ESIMS 366.1 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.98(d, J = 2.6 Hz, 1H), 8.64 (dd, J = 4.7, 1.3 Hz, 1H), 8.08 (s, 1H), 8.03(ddd, J = 8.3, 2.7, 1.4 Hz, 1H), 7.55-7.39 (m, 1H), 3.92 (s, 2H), 3.80(s, 2H), 3.71 (q, J = 7.1 Hz, 2H), 3.32 (t, J = 7.3 Hz, 2H), 1.17 (t, J= 7.2 Hz, 3H) IR (thin film) 1658 cm⁻¹ F11

Colorless Solid 51-53° C. ESIMS 421 ([M + H]⁺, 419 ([M − H]⁻) (400 MHz,CDCl₃) δ 8.97 (s, 1H), 8.64 (dd, J = 4.7, 1.3 Hz, 1H), 8.06 (s, 1H),7.98 (s, 1H), 7.47 (dd, J = 8.2, 4.8 Hz, 1H), 3.55 (m, 5H), 3.22 (m,1H), 2.95 (d, J = 8.5 Hz, 1H), 2.18 (m, 1H), 1.94 (s, 1H), 1.43 (s, 9H),1.16 (t, J = 7.1 Hz, 3H) F12

Off-White Semi-Solid HRMS-ESI [M + H]⁺ calcd for C₁₇H₂₀ClF₃N₅O₂,418.1252; found, 418.1260 (400 MHz, CDCl₃) δ 8.94 (d, J = 2.6 Hz, 1H),8.64 (dd, J = 4.8, 1.4 Hz, 1H), 8.04 (ddd, J = 8.3, 2.7, 1.4 Hz, 1H),7.93 (s, 1H), 7.47 (ddd, J = 8.3, 4.8, 0.8 Hz, 1H), 6.41 (t, J = 5.8 Hz,1H), 3.71 (q, J = 7.2 Hz, 2H), 3.51 (q, J = 6.0 Hz, 2H), 2.55-2.37 ¹⁹FNMR (376 MHz, CDCl₃) δ −66.70 IR (thin film) 3317, 3087, 1656 m⁻¹(multiple peaks, 4H), 2.37- 2.31 (m, 2H), 1.17 (t, J = 7.2 Hz, 3H) F13

Slightly Yellow Solid HRMS-ESI [M + H]⁺ calcd for C₂₀H₂₃ClN₅O₃,416.1484; found, 416.1476 (400 MHz, CDCl₃) δ 8.98- 8.93 (m, 1H), 8.62(dd, J = 4.7, 1.4 Hz, 1H), 8.06-7.97 (multiple peaks, 2H), 7.45 (ddd, J= 8.4, 4.8, 0.8 Hz, 1H), 6.09 (d, J = 3.1 Hz, 1H), 6.07-5.97 (m, 1H),5.88 (dt, J = 3.1, 1.1 Hz, 1H), 4.35 (d, J = 5.4 Hz, 2H), 3.70 (q, J =7.1 Hz, IR (thin flim) 3302, 3087, 1655 cm⁻¹ 2H), 2.51 (br s, 4H), 2.33-2.17 (m, 3H), 1.14 (t, J = 7.2 Hz, 3H) F14

Light Brown Gum ESIMS 492 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.89 (d, J = 2.4Hz, 1H), 8.57 (d, J = 4.4 Hz, 1H), 7.80-7.97 (m, 1H), 7.92 (s, 1H), 7.52(d, J = 8.0 Hz, 2H), 7.40 (dd, J = 8.4 Hz, 4.8 Hz, 1H), 7.27 (d, J = 8.4Hz, 2H), 4.38- 4.29 (m, 2H), 3.61 (q, J = 6.8 Hz, 2H), 3.51-3.49 (m, IR(KBr): 3089, 2926, 2308, 1745, 1666, 1440, 1325, 1120 cm−1 1H), 3.40 (t,J = 5.6 Hz, 1H), 2.96-2.95 (m, 1H), 2.65 (dd, J = 17.2 Hz, 4.4 Hz, 1H),2.36-2.28 (m, 1H), 1.07 (t, J = 7.2 Hz, 3H) F15

Light Yellow Solid HRMS-ESI [M + H]⁺ calcd for C₂₀H₂₃ClN₅O₃, 416.1484;found, 416.1476 (400 MHz, CDCl₃) δ 8.98- 8.93 (m, 1H), 8.62 (dd, J =4.7, 1.4 Hz, 1H), 8.06-7.97 (multiple peaks, 2H), 7.45 (ddd, J = 8.4,4.8, 0.8 Hz, 1H), 6.09 (d, J = 3.1 Hz, 1H), 6.07-5.97 (m, 1H), 5.88 (dt,J = 3.1, 1.1 Hz, 1H), 4.35 (d, J = 5.4 Hz, 2H), 3.70 (q, J = 7.1 Hz,2H), 2.51 (br s, 4H), 2.33-2.17 13C NMR (101 MHz, CDCl₃) δ 172.41,172.02, 148.61, 140.81, 140.13, 135.66, 126.63, 126.31, 124.05, 123.82,45.78, 43.97, 37.93, 31.50, 30.79 29.66, 26.39 (m, 3H) 1.14 (t, J = 7.2Hz, 25.83, 13.08 3H) IR (thin film) 3315, 3087, 1653 cm⁻¹ F16

Colorless Oil ESIMS 382 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.99 (d, J = 2.6Hz, 1H), 8.61 (dd, J = 4.7, 1.4 Hz, 1H), 8.24 (s, 1H), 8.02 (ddd, J =8.3, 2.7, 1.4 Hz, 1H), 7.43 (ddd, J = 8.3, 4.8, 0.5 Hz, 1H), 5.02 (q, J= 6.7 Hz, 1H), 3.98 (s, 1H), 3.72 (s, 3H), 3.39 (s, 1H), 3.16 (s, 3H),1.40 (d, J = 6.8 Hz, 3H), 1.16 (t, J = 7.2 Hz, 3H) IR (thin film) 2977,2936, 1676 m⁻¹ F17

Colorless Gum (400 MHz, CDCl₃) δ 8.95 (dd, J = 2.7, 0.7 Hz, 1H), 8.64(dd, J = 4.7, 1.4 Hz, 1H), 8.04 (ddd, J = 8.3, 2.7, 1.4 Hz, 1H), 7.93(s, 1H), 7.88 (t, J = 1.1 Hz, 1H), 7.47 (ddd, J = 8.3, 4.7, 0.7 Hz, 1H),7.24 (t, J = 1.5 Hz, 1H), 7.11 (dd, J = 1.6, 0.9 Hz, 1H), 6.28-5.73 (m,1H), 3.92-3.79 (m, 4H), 3.70 (q, ¹⁹F NMR (376 MHz, CDCl₃) δ −121.88 IR(thin film) 1638 cm⁻¹ J = 7.2 Hz, 2H), 2.50 (t, J = 6.4 Hz, 2H), 1.16(t, J = 7.2 Hz, 3H) F18

Off-White Solid 131-133° C. ESIMS 430.2 ([M + H]⁺) (400 MHz, CDCl₃) δ8.97 (d, J = 2.5 Hz, 1H), 8.61 (dd, J = 4.7, 1.4 Hz, 1H), 8.13 (s, 1H),8.04 (ddd, J = 8.3, 2.7, 1.5 Hz, 1H), 7.44 (ddd, J = 8.3, 4.8, 0.5 Hz,1H), 3.54 (d, J = 6.8 Hz, 2H), 3.48 (dd, J = 12.3, 6.9 Hz, 4H), 2.60 (d,J = 58.7 Hz, 4H), 1.79- 1.67 (m, 4H), 1.55 (dd, J = 6.4, 3.8 Hz, 4H),1.04-0.85 (m, 1H), 0.57-0.40 (m, 2H), IR (thin film) 1638 cm⁻¹ 0.24-0.09(m, 2H) F19

White Solid HRMS-ESI [M + Na]+ calcd for C₁₈H₂₄ClN₅NaO₃, 416.1460;found, 416.1459 (400 MHz, CDCl₃) δ 8.95 (s, 1H), 8.63 (d, J = 4.6 Hz,1H), 8.05 (ddd, J = 8.3, 2.7, 1.5 Hz, 1H), 7.95 (s, 1H), 7.51-7.42 (m,1H), 5.22 (s, 1H), 3.71 (q, J = 7.2 Hz, 2H), 3.38 (q, J = 6.0 Hz, 2H),2.33 (t, J = 5.8 Hz, 2H), 1.41 (s, 9H), 1.16 (t, J = 7.2 Hz, 3H) IR(thin film) 3346, 3093, 1697, 1661 cm⁻¹ F20

Colorless Oil ESIMS 440.2 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.95 (dt, J =2.2, 1.0 Hz, 1H), 8.62 (dd, J = 4.8, 1.5 Hz, 1H), 8.04 (ddd, J = 8.3,2.8, 1.5 Hz, 1H), 7.93 (S, 1H), 7.45 (ddd, J = 8.3, 4.7, 0.7 Hz, 1H),4.03 (t, J = 6.3 Hz, 2H), 3.70 (q, J = 7.1 Hz, 2H), 2.51 (dd, J = 8.5,6.9 Hz, 2H), 2.41-2.31 (m, 2H), 1.81 (s, 3H), 1.80 (m, 1H), 1.71 (ddd, J= 17.0, 8.7, 5.3 Hz, 1H), 1.52 (m, 1H), 1.44- 1.28 (m, 1H), 1.21-1.08(m, IR (thin film) 3092, 2968, 2932, 1662 cm⁻¹ 3H), 0.89 (dtd, J = 12.8,7.5, 3.5 Hz, 1H) F21

Off-White Solid 108-110° C. ESIMS 390.2 ([M + H]⁺) (400 MHz, CDCl₃) δ8.97 (d, J = 2.6 Hz, 1H), 8.61 (dd, J = 4.7, 1.4 Hz, 1H), 8.12 (s, 1H),8.03 (ddd, J = 8.3, 2.7, 1.4 Hz, 1H), 7.44 (ddd, J = 8.3, 4.8, 0.6 Hz,1H), 3.71 (q, J = 7.2 Hz, 2H), 3.57- 3.46 (m, 2H), 3.46-3.39 (m, 2H),2.65 (d, J = 6.1 Hz, 2H), 2.48 (d, J = 6.0 Hz, 2H), 1.65-1.50 (m, 6H),1.15 (t, J = 7.2 Hz, 3H) IR (thin film) 1624 cm⁻¹ F22

Off-White Solid 145-148° C. ESIMS 362.1 ([M + H]⁺) (400 MHz, CDCl₃) δ8.97 (d, J = 2.5 Hz, 1H), 8.62 (dd, J = 4.7, 1.3 Hz, 1H), 8.17 (s, 1H),8.01 (ddd, J = 8.3, 2.7, 1.4 Hz, 1H), 7.44 (dd, J = 8.3, 4.8 Hz, 1H),4.02 (s, 2H), 3.46 (s, 2H), 3.24 (s, 3H), 2.57-2.45 (m, 2H), 1.78-1.64(m, 6H) IR (thin film) 1678, 1628 cm⁻¹ F23

White Solid ESIMS 304 ([M − BOC]⁺) (400 MHz, CDCl₃) δ 8.96 (bs, 1H),8.63 (dd, J = 4.9 Hz, 1H), 8.21-7.86 (m, 2H), 7.46 (dd, J = 8.3, 4.8 Hz,1H), 4.65-4.30 (m, 2H). 4.02-3.70 (bs, 2H), 3.06- 2.79 (m, 3H), 2.25(bs,1H), 1.44(s, 9H) IR (thin film) 1696 cm⁻¹ F24

White Foam ESIMS 360 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.97 (d, J = 2.6 Hz,1H), 8.63 (dd, J = 4.8, 1.4 Hz, 1H), 8.12 (s, 1H), 8.07 (ddd, J = 8.3,2.7, 1.5 Hz, 1H), 7.48 (dd, J = 8.3, 4.8 Hz, 1H), 6.74 (d, J = 9.0 Hz,1H), 5.91 (dt, J = 5.5, 2.2 Hz, 1H), 5.73 (ddd, J = 5.5, 2.5, 1.1 Hz,1H), 5.05 (dddd, J = 9.6, 7.0, ¹³C NMR (101 MHz, CDCl₃) δ 175.49,169.10, 148.61, 139.94, 135.58, 134.80, 134.75, 131.43, 126.34, 126.32,125.50, 124.13, 54.05, 47.37, 37.49, 3.4, 1.7 Hz, 1H), 3.57 (dq, 35.19,23.46 J = 8.3, 2.3 Hz, 1H), 3.26 (s, 3H), 2.25 (dt, J = 13.8, 8.3 Hz,1H), 1.99 (s, 3H), 1.87 (dt, J = 13.8, 2.3 Hz, 1H) F25

White Solid 123-136° C. (400 MHz, CDCl₃) δ 8.96 (d, J = 2.4 Hz, 1H),8.61 (dd, J = 4.7, 1.4 Hz, 1H), 8.19 (s, 1H), 8.02 (ddd, J = 8.3, 2.7,1.5 Hz, 1H), 7.44 (ddd, J = 8.3, 4.8, 0.6 Hz, 1H), 3.24 (s, 3H), 3.04(s, 3H), 2.93 (s, 3H), 2.67 (t, J = 6.3 Hz, 2H), 2.51 (t, J = 6.3 Hz,2H) ¹³C NMR (101 MHz, CDCl₃) δ 173.2, 171.8, 148.5, 140.1, 135.7, 126.5,126.3, 125.8, 124.0, 37.1, 36.9, 35.5, 28.5, 28.4 IR (thin film) 3431,1629, 1585 cm⁻¹ F26

White Semi- Solid ESIMS 306.1 ([M + H − Boc]⁺) (400 MHz, CDCl₃) δ 8.94(dd, J = 2.8, 0.8 Hz, 1H), 8.64 (dd, J = 4.7, 1.4 Hz, 1H), 8.03 (ddd, J= 8.4, 2.7, 1.4 Hz, 1H), 7.90 (s, 1H), 7.47 (ddd, J = 8.3, 4.8, 0.8 Hz,1H), 4.24-4.09 (m, 2H), 3.86-3.65 (m, 4H), 3.32 (tt, J = 8.8, 6.4 Hz,1H), 1.41 (s, 9H), 1.17 (t, J = 7.2 Hz, 3H) IR (thin film) 1670 cm⁻¹ F27

White Solid 99-101° C. ESIMS 390.2 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.96(d, J = 2.6 Hz, 1H), 8.60 (dd, J = 4.7, 1.4 Hz, 1H), 8.18 (s, 1H), 8.02(ddd, J = 8.3, 2.7, 1.5 Hz, 1H), 7.44 (ddd, J = 8.4, 4.8, 0.5 Hz, 1H),3.51- 3.45 (m, 4H), 3.24 (s, 3H), 2.68 (t, J = 6.4 Hz, 2H), 2.53 (t, J =6.4 Hz, 2H), 1.75 (dd, J = 11.3, 5.7 Hz, 2H), 1.68 (dd, J = 11.4, 5.6Hz, 2H), 1.60-1.52 (m, 4H) IR (thin filim) 1658 cm⁻¹ F28

Off-White Foam HRMS-ESI [M + H]⁺ calcd for C₁₈H₂₂ClF₃N₅O₂ 432.1409;found 432.1420 (400 MHz, CDCl₃) δ 8.94 (d, J = 2.7 Hz, 1H), 8.64 (dd, J= 4.8, 1.4 Hz, 1H), 8.05 (ddd, J = 8.3, 2.7, 1.4 Hz, 1H), 7.93 (s, 1H),7.47 (ddd, J = 8.4, 4.8, 0.8 Hz, 1H), 6.41 (t, J = 6.0 Hz, 1H),3.81-3.61 (m, 2H), 3.60- 3.40 (m, 2H), 2.83 (tddd, J = 9.0, 7.0, 4.5,2.1 Hz, ¹⁹F NMR (376 MHz, CDCl₃) δ −73.55 IR (thin film) 3323, 3088,1655 cm⁻¹ 1H), 2.51 (dd, J = 14.8, 4.8 Hz, 1H), 2.41-2.27 (m, 2H), 2.08(dd, J = 14.8, 9.1 Hz, 1H), 1.17 (t, J = 7.2 Hz, 3H), 1.14 (d, J = 6.9Hz, 3H) F29

White Semi- Solid ESIMS 362.2 ([M + H]⁺) (400 MHz, CDCl₃) δ 9.01- 8.92(m, 1H), 8.64 (dd, J = 4.8, 1.5 Hz, 1H), 8.06 (ddd, J = 8.4, 2.7, 1.4Hz, 1H), 8.01 (s, 1H), 7.53-7.40 (m, 1H), 4.55 (d, J = 13.3 Hz, 1H),3.82 (d, J = 13.5 Hz, 1H), 3.23 (s, 3H), 3.02-2.85 (m, 1H), 2.63-2.38(m, 2H), IR (thin film) 1630 cm⁻¹ 2.07 (s, 3H), 1.94-1.64 (m, 4H) F30

Light Yellow Clear Viscous Oil HRMS-ESI [M + H]⁺ calcd for C₁₉H₂₅ClN₅O₂,390.1691; found, 390.1695. (400 MHz, CDCl₃) δ 8.98 (s, 1H), 8.61 (s,1H), 8.12 (d, J = 0.6 Hz, 1H), 8.09- 7.98 (m, 1H), 7.45 (dd, J = 8.4,4.7 Hz, 1H), 3.71 (q, J = 7.1 Hz, 2H), 3.23 (t, J = 7.2 Hz, 2H), 3.02(d, J = 43.3 Hz, 3H), 2.67 (br s, 2H), 2.49 (br s, 2H), 1.15 (td, J =7.2, 0.8 Hz, 3H), 1.03-0.85 (m, 1H), 0.62-0.53 IR (thin film) 3081, 1642cm⁻¹ (m, 1H), 0.51-0.44 (m, 1H), 0.22 (ddt, J = 11.9, 6.1, 4.7 Hz, 2H)F31

Colorless Oil ESIMS 350 ([M + H]⁺). (400 MHz, CDCl₃) δ 8.97 (d, J = 2.7Hz, 1H), 8.62 (dd, J = 4.8, 1.5 Hz, 1H), 8.08 (s, 1H), 8.03 (ddd, J =8.3, 2.7, 1.5 Hz, 1H), 7.45 (dd, J = 8.5, 4.7 Hz, 1H), 4.35-4.25 (m,2H), 3.75-3.63 (m, 2H), 3.53 (t, J = 6.5 Hz, 2H), 3.24 (s, 3H), 2.53 (t,J = 6.5 Hz, 2H) IR (thin film) 3095, 2921, 1734, 1659 cm⁻¹ F32

Light Green Gum ESIMS 348 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.95 (d, J = 2.4Hz, 1H), 8.63 (d, J = 4.0 Hz, 1H), 8.05-8.02 (m, 1H), 7.98 (s, 1H), 7.46(dd, J = 8.4 Hz, 4.8 Hz, 1H), 3.67 (q, J = 7.2 Hz, 2H), 3.53-3.52 (m,2H), 3.06 (d, J = 3.6 Hz, 1H), 2.80 (s, 3H), 2.72(dd, J = 16.8 Hz, 3.6Hz, 1H), 2.42-2.35 (m, 1H), 1.16 (t, J = 7.2 Hz, 3H) IR (KBr): 34392924, 1743, 1666, 1440, 1261 cm⁻¹ F33

White Solid 129-131° C. ESIMS 376.2 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.96(d, J = 2.5 Hz, 1H), 8.60 (dd, J = 4.7, 1.4 Hz, 1H), 8.18 (s, 1H), 8.02(ddd, J = 8.3, 2.7, 1.4 Hz, 1H), 7.44 (ddd, J = 8.3, 4.7, 0.5 Hz, 1H),3.53- 3.41 (m, 4H), 3.24 (s, 3H), 2.67 (t, J = 6.4 Hz, 2H), 2.51 (t, J =6.4 Hz, 2H), 1.64- 1.50 (m, 6H) IR (thin film) 1630 cm⁻¹ F34

Colorless Oil ESIMS 462.2 ([M + H]⁺) (400 MHz, CDCl₃) δ 9.08- 8.83 (m,1H), 8.63 (ddd, J = 7.0, 4.8, 1.5 Hz, 1H), 8.03 (ddd, J = 8.4, 2.7, 1.4Hz, 1H), 7.92 (d, J = 9.3 Hz, 1H), 7.52-7.38 (m, 1H), 6.16-5.70 (m, 1H),4.02 (m, 1H), 3.82-3.47 (m, 5H), 2.89 (m, 1H), 2.67-2.50 (m, 1H), 2.45(d, J = 5.7 Hz, IR (thin film) 3098, 2977, 1650 cm⁻¹ 1H), 2.24-2.09 (m,1H), 1.78-1.60 (m, 1H), 1.21- 1.09 (m, 3H) F35

Light Brown Oil ESIMS 476.3 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.95 (d, J =2.7 Hz, 1H), 8.63 (dt, J = 4.7, 2.4 Hz, 1H), 8.17- 8.02 (m, 1H),8.02-7.90 (m, 1H), 7.46 (ddd, J = 8.1, 4.8, 2.8 Hz, 1H), 6.34-5.66 (m,1H), 4.02-3.28 (m, 6H), 2.48 (t, J = 7.6 Hz, 1H), 1.85 (ddd, J = 13.6,8.3, 4.5 Hz, 1H), 1.44 (dt, J = 5.2, 2.3 IR (thin film) 3096, 2977, 1650cm⁻¹ Hz, 3H), 1.35-0.98 (m, 5H) F36

Colorless Oil ESIMS 481.3 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.94 (dd, J =5.6, 2.6 Hz, 1H), 8.61 (dd, J = 4.7, 1.4 Hz, 1H), 8.38 (d, J = 5.1 Hz,1H), 8.05 (s, 1H), 8.03- 7.97 (m, 1H), 7.49-7.39 (m, 1H), 7.36 (d, J =1.4 Hz, 1H), 7.18 (dt, J = 5.1, 1.0 Hz, 1H), 3.74 (q, J = 7.2 Hz, 2H),2.82 (t, J = 7.4 Hz, 0.6H), 2.73 (t, J = 6.7 Hz, 1.4H), 2.53 (t, J = 6.7Hz, 2H), 2.19-2.03 (m, 3H), 1.21-1.04 (m, 3H) IR (thin film) 3089, 2974,1665 cm⁻¹ F37

White Solid 116-118° C. ESIMS 362.1 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.96(d, J = 2.5 Hz, 1H), 8.60 (dd, J = 4.7, 1.4 Hz, 1H), 8.20 (s, 1H), 8.02(ddd, J = 8.4, 2.7, 1.4 Hz, 1H), 7.44 (ddd, J = 8.3, 4.8, 0.4 Hz, 1H),3.49- 3.43 (m, 4H), 3.24 (s, 3H), 2.66-2.58 (m, 2H), 2.52 (t, J = 6.2Hz, 2H), 1.95 (dd, J = 13.2, 6.7 Hz, 2H), 1.85 (dd, J = 13.5, 6.5 Hz,2H) IR (thin film) 1648, 1622 cm⁻¹ F38

Colorless Gum ESIMS 366.7 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.97 (d, J = 2.8Hz, 1H), 8.63 (dd, J = 4.8, 1.5 Hz, 1H), 8.10 (s, 1H), 8.03 (ddd, J =8.4, 2.8, 1.5 Hz, 1H), 7.45 (dd, J = 8.5, 4.7 Hz, 1H), 4.57-4.43 (m,2H), 3.98 (dd, J = 9.5, 8.0 Hz, 2H), 3.86 (t, J = 6.3 Hz, 2H), 3.24 (s,3H), 2.72 (t, J = 6.3 Hz, 2H) IR (thin film) 3094, 2933, 1659 cm⁻¹ F39

Colorless Oil ESIMS 362.1 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.99 (d, J = 2.5Hz, 1H), 8.62 (dd, J = 4.7, 1.4 Hz, 1H), 8.11 (s, 1H), 8.05 (ddd, J =8.4, 2.7, 1.5 Hz, 1H), 7.45 (ddd, J = 8.4, 4.8, 0.5 Hz, 1H), 3.68 (dd, J= 14.2, 7.2 Hz, 2H), 3.53 (t, J = 6.9 Hz, 2H), 3.46 (t, J = 7.1 Hz, 2H),2.43 (t, J = 6.9 Hz, 2H), 2.33 (t, J = 8.1 Hz, 2H), 2.06-1.96 (m, IR(thin film) 1658 cm⁻¹ 2H), 1.15 (t, J = 7.2 Hz, 3H) F40

Light Yellow Oil ESIMS 397 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.99 (d, J =2.5 Hz, 1H), 8.62 (d, J = 4.7 Hz, 1H), 8.07 (m, 2H), 7.46 (dd, J = 8.2,4.8 Hz, 1H), 3.68 (m, 4H), 3.00 (s, 3H), 2.79 (s, 2H), 2.44 (s, 2H),1.21 (m, 6H) IR (thin film) 3387, 3089, 2973, 2931 cm⁻¹ F41

Yellow Oil (400 MHz, CDCl₃) δ 8.94 (d, J = 2.6 Hz, 1H), 8.61 (dd, J =4.8, 1.5 Hz, 1H), 8.03 (ddd, J = 8.3, 2.7, 1.5 Hz, 1H), 8.00 (s, 1H),7.46 (dd, J = 8.3, 4.8 Hz, 1H), 5.80 (d, J = 6.5 Hz, 1H), 4.46 (qt, J =7.6, 3.8 Hz, 1H), 3.30 (s, 3H), 2.83-2.69 (m, 2H), 2.44-2.31 (m, 1H),2.28- ¹³C NMR (101 MHz, CDCl₃) δ 169.59, 167.84, 148.61, 140.02, 139.88,136.66, 135.60, 126.60, 125.37, 124.14, 55.44, 48.71, 41.08, 40.65,23.30 2.18 (m, 1H), 1.88 (s, 3H) (two aromatic carbon not located) IR(thin film) 3287, 3080, 2920, 2849, 1646, 1584, 1545 cm⁻¹ F42

Colorless Oil ESIMS 381 ([M + H]⁺) (400 MHz, CDCl₃) δ 9.00 (d, J = 2.6Hz, 1H), 8.62 (d, J = 4.3 Hz, 1H), 8.06 (m, 2H), 7.46 (s, 1H), 4.02 (m,2H), 3.70 (q, J = 6.9 Hz, 2H), 3.54 (t, J = 7.0 Hz, 2H), 2.89 (s, 3H),2.41 (m, 2H), 1.19 (m, 6H) IR (thin film) 2978, 1660 1584 cm⁻¹ F43

Clear Semi- Solid HRMS-ESI [M + H]⁺ calcd for C₁₆H₂₀ClFN₅O₂, 368.1284;found, 368.1304 (400 MHz, CDCl₃) δ 8.96 (d, J = 2.7 Hz, 1H), 8.62 (dd, J= 4.8, 1.5 Hz, 1H), 8.07- 8.00 (m, 2H), 7.46 (dd, J = 8.3, 4.8 Hz, 1H),6.23 (br s, 1H), 4.54 (t, J = 4.8 Hz, 1H), 4.42 (t, J = 4.8 Hz, 1H),3.70 (q, J = 7.2 Hz, 2H), 3.63- 3.56 (m, 1H), 3.52 (q, J = IR (thinfilm) 3316, 3087, 1652 cm⁻¹ 5.1 Hz, 1H), 2.52 (q, J = 5.4 Hz, 4H), 1.15(t, J = 7.2 Hz, 3H) F44

Off-White Foam HRMS-ESI ([M + H]⁺ calcd for C18H22ClF3N5O2, 432.1409;found, 432.1422 (400 MHz, CDCl₃) δ 8.94 (d, J = 2.6 Hz, 1H), 8.63 (dd, J= 4.7, 1.4 Hz, 1H), 8.03 (ddd, J = 8.3, 2.7, 1.4 Hz, 1H), 7.91 (s, 1H),7.46 (ddd, J = 8.3, 4.8, 0.8 Hz, 1H), 6.44 (t, J = 5.9 Hz, 1H), 3.70(ddt, J = 31.2, 13.6, 6.9 Hz, 2H), 3.62-3.37 (m, 2H), 2.66 ¹⁹F NMR (376MHz, CDCl₃) δ −64.77 IR (thin film) 3320, 3088, 1655 cm⁻¹ (dqd, J =14.8, 10.9, 8.6 Hz, 1H), 2.55-2.44 (m, 1H), 2.44-2.25 (m, 2H), 2.18-2.00 (m, 1H), 1.26-1.20 (m, 3H), 1.17 (t, J = 7.2 Hz, 3H) F45

Orange Oil ESIMS 420 (M + H)+ (400 MHz, CDCl₃) d 8.95 (dd, J = 2.7, 0.8Hz, 1H), 8.63 (dd, J = 4.8, 1.4 Hz, 1H), 8.05 (ddd, J = 8.4, 2.8, 1.5Hz, 1H), 7.99 (s, 1H), 7.47 (ddd, J = 8.3, 4.8, 0.8 Hz, 1H), 5.60 (d, J= 8.0 Hz, 1H), 4.03 (s, 1H), 3.24 (s, 3H), 2.86 (t, J = 4.8 Hz, 1H),2.03-1.84 (m, 2H), 1.80-1.64 (m, 4H), 1.44 (s, ¹³C NMR (101 MHz, CDCl₃)d 178.09, 155.42, 148.68, 140.44, 139.97, 135.62, 126.31, 125.98,125.74, 124.13, 78.89, 52.36, 39.73, 37.35, 36.86, 34.02, 29.04 (9H)28.48 F46

White Solid HRMS-ESI [M + H]⁺ calcd for C₂₁H₂₂ClFN₅O₂, 430.1441; found430.1445 (400 MHz, CDCl₃) δ 9.03- 8.86 (m, 1H), 8.63 (dd, J = 4.8, 1.4Hz, 1H), 8.02 (ddd, J = 8.3, 2.7, 1.4 Hz, 1H), 7.86 (s, 1H), 7.46 (ddd,J = 8.4, 4.7, 0.7 Hz, 1H), 7.26- 7.19 (m, 2H), 7.09-6.97 (m, 2H),6.33-6.22 (m, 1H), 3.66 (q, J = 7.2 Hz, 2H), 3.55-3.39 (multiple peaks,4H), 2.31 (t, J = 5.7 Hz, 2H), 1.14 (t, J = 7.2 Hz, 3H) ¹⁹F NMR (376MHz, CDCl₃) δ −115.49 IR (thin film) 3302, 3071, 1651 cm⁻¹ F47

Off-White Solid 109-112° C. ESIMS 362.1 ([M + H]⁺) (400 MHz, CDCl₃) δ8.99 (d, J = 2.6 Hz, 1H), 8.62 (dd, J = 4.8, 1.4 Hz, 1H), 8.15 (s, 1H),8.02 (ddd, J = 8.3, 2.7, 1.4 Hz, 1H), 7.45 (dd, J = 8.4, 4.7 Hz, 1H),3.92 (s, 2H), 3.73-3.66 (m, 2H), 3.47-3.33 (m, 2H), 2.47- 2.26 (m, 2H),1.88-1.82 (m, 4H), 1.17 (t, J = 7.2 Hz, 3H) IR (thin film) 1672, 1627cm⁻¹ F48

White Solid 126-129° C. ESIMS 350.1 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.98(d, J = 2.6 Hz, 1H), 8.64 (dd, J = 4.7, 1.3 Hz, 1H), 8.09 (s, 1H), 8.03(ddd, J = 8.4, 2.7, 1.4 Hz, 1H), 7.46 (ddd, J = 8.3, 4.8, 0.5 Hz, 1H),4.39 (t, J = 8.0 Hz, 2H), 3.87 (s, 2H), 3.81-3.60 (m, 4H), 1.17 (t, J =7.2 Hz, 3H) IR (thin film) 1736, 1669 cm⁻¹ F49

Colorless Oil ESIMS 362.1 ([M + H]⁺) (400 MHz, CDCl₃) δ 9.00 (d, J = 2.5Hz, 1H), 8.61 (dd, J = 4.7, 1.3 Hz, 1H), 8.15 (s, 1H), 8.06 (ddd, J =8.4, 2.7, 1.5 Hz, 1H), 7.44 (ddd, J = 8.3, 4.8, 0.6 Hz, 1H), 3.60 (t, J= 7.1 Hz, 2H), 3.37 (t, J = 5.6 Hz, 2H), 3.22 (s, 3H), 2.50 (t, J = 7.1Hz, 2H), 2.32 (dd, J = 12.2, 5.8 Hz, 2H), 1.80-1.76 (m, 4H) IR (thinfilm) 1661, 1619 cm⁻¹ F50

Light Yellow Gum ESIMS 348 ([M + H]⁺) (400 MHz, CDCl₃) δ 9.01 (d, J =2.4 Hz, 1H), 8.64 (d, J = 4.0 Hz, 1H), 8.09-8.06 (m, 2H), 7.47 (dd, J =8.4 Hz, 4.8 Hz, 1H), 5.59 (s, 1H), 3.76-3.66 (m, 2H), 3.45 (t, J = 5.6Hz, 1H), 3.28- 3.26 (m, 1H), 3.00 (dd, J = 5.6, 2.5 Hz, 1H), 2.45-2.33(m, 2H), 2.19-2.09 (m, 1H), IR (KBr): 3435, 2974, 2829, 1743, 1658,1487, 1357, 1180 cm−1 2.06-1.97 (m, 1H), 1.18 (t, J = 7.2 Hz, 3H) F51

Colorless Oil ESIMS 418.2 ([M + H]⁺) (400 MHz, CDCl₃) δ 9.00- 8.90 (m,1H), 8.62 (dd, J = 4.7, 1.4 Hz, 1H), 8.03 (ddd, J = 8.3, 2.8, 1.6 Hz,1H), 7.91 (d, J = 4.9 Hz, 1H), 7.45 (ddd, J = 8.3, 4.7, 0.8 Hz, 1H),4.38-4.24 (m, 2H), 3.70 (q, J = 7.2 Hz, 2H), 2.53 (t, J = 7.0 Hz, 2H),2.38 (t, J = 7.4 Hz, 2H), 1.86 (s, 3H), 1.15 (dd, J = 7.8, 6.7 Hz, 3H)IR (thin film) 3092, 2974, 2932, 1663 cm⁻¹ F52

Brown Viscous Oil HRMS-ESI [M + H]⁺ calcd for C1₉H₂₇ClN₅O₃, 408.1797;found, 408.1802 (400 MHz, CDCl₃) δ 8.99 (d, J = 2.6 Hz, 1H), 8.62 (dt, J= 4.7, 1.5 Hz, 1H), 8.15- 8.01 (multiple peaks, 2H), 7.51-7.36 (m, 1H),3.70 (q, J = 7.0 Hz, 2H), 3.50 (t, J = 7.0 Hz, 2H), 2.84 (br s, 3H),2.39 (br s, 2H), 1.37 (br s, 9H), 1.15 (t, J = 7.2 Hz, 3H) IR (thinfilm) 3512, 3092, 1667 cm⁻¹ F53

Light Yellow Gum ESIMS 376 ([M + H]⁺) (400 MHz, CDCl₃) δ 9.02 (d, J =2.4 Hz, 1H), 8.64 (d, J = 4.0 Hz, 1H), 8.11-8.08 (m, 1H), 8.03 (s, 1H),7.48 (dd, J = 8.4 Hz, 4.8 Hz, 1H), 3.74-3.67 (m, 2H), 3.34 (t, J = 5.2Hz, 1H), 3.14-3.12 (m, 1H), 2.95 (dd, J = 5.6 Hz, 2.4 Hz, 1H), 2.80 (s,3H), 2.22 (t, J = 6.0 Hz, 2H), 1.76-1.71 (m, 4H), 1.17 (t, J = 7.2 Hz,3H) IR (KBr): 3091, 2929, 1739, 1666, 1487, 1440, 1257, 1089 cm⁻¹ F54

White Semi Solid HRMS-ESI [M + H]+ calcd for C₁₈H₂₀ClF₃N₅O₂, 430.1252;found, 430.1266 (400 MHz, CDCl₃) δ 9.03- 8.94 (m, 1H), 8.62 (dd, J =4.8, 1.5 Hz, 1H), 8.07-7.97 (multiple peaks, 2H), 7.45 (ddd, J = 8.4,4.7, 0.8 Hz, 1H), 6.17 (br s, 1H), 3.80- 3.60 (m, 2H), 3.03 (ddt, J =8.0, 4.8, 3.2 Hz, 1H), 2.56- 2.38 (m, 3H), 1.68 (dtd, J = 9.8, 6.5, 3.3Hz, 1H), 1.30- 1.19 (m, 2H), 1.15 (t, J = ¹⁹F NMR (376 MHz, CDCl₃) δ−66.34 IR (thin film) 3294, 3091, 1653 cm⁻¹ 7.2 Hz, 3H), 1.04 (dt, J =10.9, 5.8 Hz, 1H) F55

Brown Viscous Semi-Solid HRMS-ESI [M + H]⁺ calcd for C₁₇H₂₀ClN₆O₂,375.1331; found, 375.1336 (400 MHz, CDCl₃) δ 9.03- 8.94 (m, 1H), 8.62(dd, J = 4.7, 1.4 Hz, 1H), 8.09 (s, 1H), 8.04 (ddd, J = 8.3, 2.7, 1.5Hz, 1H), 7.45 (ddd, J = 8.3, 4.8, 0.8 Hz, 1H), 4.33 (s, 2H), 3.70 (q, J= 7.2 Hz, 2H), 3.18 (s, 3H), 2.77-2.61 (m, 2H), 2.58-2.42 (m, 2H), 1.16(t, J = 7.2 Hz, 3H) IR (thin film) 3503, 3094, 2247, 1653 cm⁻¹ F56

Light Brown Solid HRMS-ESI [M + H]⁺ calcd for C₁₇H₁₉ClF₂N₅O₂, 398.1190;found, 398.1208 (400 MHz, CDCl₃) δ 8.94 (dd, J = 2.7, 0.7 Hz, 1H), 8.63(dd, J = 4.8, 1.5 Hz, 1H), 8.03 (ddd, J = 8.4, 2.7, 1.5 Hz, 1H), 7.94(s, 1H), 7.46 (ddd, J = 8.3, 4.8, 0.8 Hz, 1H), 6.66-6.50 (m, 1H), 3.73(dh, J = 13.8, 7.0 Hz, 2H), 3.63-3.44 (m, 2H), 2.38 (qdd, J = 17.0, 6.9,4.3 Hz, ¹⁹F NMR (376 MHz, CDCl₃) δ −125.72 (d, J = 153.9 Hz), −141.43(d, J = 153.9 Hz) IR (thin film) 3317, 3090, 1656 cm⁻¹ 2H), 2.24 (ddd, J= 13.0, 10.8, 7.7 Hz, 1H), 2.08 (dtd, J = 12.5, 7.7, 6.2 Hz, 1H),1.72-1.58 (m, 1H), 1.18 (t, J = 7.2 Hz, 3H) F57

White Solid HRMS-ESI [M + H]⁺ calcd for C₁₅H₁₆ClF₃N₅O₂, 390.0939; found,390.0950 (400 MHz, CDCl₃) δ 9.00- 8.90 (m, 1H), 8.65 (dd, J = 4.8, 1.5Hz, 1H), 8.05 (ddd, J = 8.4, 2.7, 1.5 Hz, 1H), 7.99 (s, 1H), 7.48 (ddd,J = 8.3, 4.8, 0.8 Hz, 1H), 6.75 (s, 1H), 3.98-3.84 (m, 2H), 3.75 (q, J =7.2 Hz, 2H), 3.12 (q, J = 10.5 Hz, 2H), 1.20 (t, J = 7.2 Hz, 3H) ¹⁹F NMR(376 MHz, CDCl₃) δ −63.03 IR (thin film) 3326, 3093, 1656 cm⁻¹ F58

Light Yellow Gum ESIMS 362 ([M + H]⁺) (400 MHz, DMSO-d₆) δ 9.08 (d, J =2.8 Hz, 1H), 8.93 (s, 1H), 8.59 (dd, J = 4.4 Hz, 1.2 Hz, 1H), 8.22 (ddd,J = 8.0 Hz, 2.4 Hz, 1.2 Hz, 1H), 7.63 (bs, 1H), 7.59 (dd, J = 12.8 Hz,4.8 Hz, 1H), 3.57 (q, J = 14.0 Hz, 6.8 Hz, 2H), 3.18 (t, J = 5.6 Hz,1H), 3.02-3.01 (m, 1H), 2.77 (dd, J = 5.2 Hz, 2.4 Hz, IR (KBr): 3277,3093, 2933, 1747, 1658, 1585, 1440, 1259 cm−1 1H), 2.11 (t, J = 6.4 Hz,2H), 1.56-1.53 (m, 4H), 1.06 (t, J = 6.8 Hz, 3H) F59

Colorless Oil ESIMS 481.3 ([M + H]⁺) ¹H NMR (400 MHz, CDCl₃) δ 9.03-8.97(m, 0.3H), 8.95-8.90 (m, 0.7H), 8.61 (ddd, J = 5.8, 4.8, 1.4 Hz, 1H),8.06-7.95 (m, 2H), 7.70-7.80 (m, 1H), 7.44 (ddd, J = 8.3, 4.8, 0.7 Hz,1H), 7.34 (m, 2H), 3.74 (q, J = 7.2 Hz, 1.4H), 3.60 (d, J = 7.4 Hz,0.6H), 2.71 (t, J = 7.0 Hz, 2H), 2.51 (t, J = 7.0 Hz, 2H), 2.12 (s,2.1H), 2.10 (s, 0.9H), 1.15 (m, 3H) IR (thin film) 3090, 2981, 1656 cm⁻¹F60

Colorless Oil ESIMS 336 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.95 (d, J = 2.2Hz, 1H), 8.62 (dd, J = 4.7, 1.2 Hz, 1H), 8.05 (ddd, J = 8.3, 2.6, 1.4Hz, 1H), 8.00 (d, J = 11.0 Hz, 1H), 7.46 (dd, J = 8.1, 4.6 Hz, 1H), 3.78(s, 3H), 3.24 (d, J = 2.8 Hz, 3H), 2.55 (ddd, J = 14.0, 8.1, 6.5 Hz,2H), 2.40. (m, 2H), 1.80 (d, J = 2.4 Hz, 3H). Mixture of E and Z isomerin 3:1 ratio, major isomer report F61

White Semi- Solid ESIMS 376.2 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.97 (d, J =2.7 Hz, 1H), 8.64 (dd, J = 4.8, 1.5 Hz, 1H), 8.07 (ddd, J = 8.3, 2.7,1.5 Hz, 1H), 7.98 (s, 1H), 7.48 (ddd, J = 8.2, 4.8, 0.8 Hz, 1H), 4.54(d, J = 13.3 Hz, 1H), 3.81 (d, J = 13.6 Hz, 1H), 3.69 (s, 2H), 3.01-2.86(m, 1H), 2.46 (td, J = 11.1, 5.4 IR (thin film) 1631 cm⁻¹ Hz, 2H), 2.07(s, 3H), 1.85- 1.64 (m, 4H), 1.15 (t, J = 7.1 Hz, 3H) F62

White Solid 98-102° C. ESIMS 316 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.95 (d,J = 2.5 Hz, 1H), 8.55 (dd, J = 4.7, 1.3 Hz, 1H), 8.03- 8.01 (m, 1.5H),8.01-7.98 (m, 0.5H), 7.40 (ddd, J = 8.3, 4.8, 0.6 Hz, 1H), 3.22 (s, 3H),3.04 (s, 3H), 2.93 (s, 3H), 2.64 (t, J = 6.4 Hz, 2H), 2.47 (t, J = 6.4Hz, 2H), 2.31 (s, 3H) ¹³C NMR (101 MHz, CDCl₃) δ 173.3, 171.7, 148.2,147.6, 140.2, 136.2, 127.4, 126.1, 124.9, 123.9, 37.2, 37.1, 35.5, 28.7,28.4, 11.1. F63

White Solid HRMS-ESI [M + H]⁺ calcd for C₁₆H₁₈ClF₃N₅O₂, 404.1096; found,404.1117 (400 MHz, CDCl₃) δ 8.98- 8.93 (m, 1H), 8.63 (dd, J = 4.8, 1.5Hz, 1H), 8.04 (ddd, J = 8.3, 2.8, 1.5 Hz, 1H), 7.93 (s, 1H), 7.46 (ddd,J = 8.4, 4.8, 0.8 Hz, 1H), 6.68 (br s, 1H), 3.71 (q, J = 7.2 Hz, 2H),3.55 (q, J = 5.9 Hz, 2H), 3.03 (q, J = 10.6 Hz, 2H), 2.45-2.32 (m, 2H),1.17 (t, J = 7.2 Hz, 3H) ¹⁹F NMR (376 MHz, CDCl₃) δ −63.08 IR (thinfilm) 3320, 3092, 1663 cm⁻¹ F64

Colorless Oil ESIMS 350 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.98 (m, 1H), 8.60(ddd, J = 8.9, 4.7, 1.3 Hz, 1H), 8.09 (s, 1H), 8.04 (ddd, J = 8.4, 2.7,1.4 Hz, 1H), 7.44 (ddd, J = 9.7, 8.5, 4.7 Hz, 1H), 3.65 (ddt, J = 36.1,21.7, 7.1 Hz, 4H), 2.91 (d, J = 96.1 Hz, 3H), 2.40 (dt, J = 9.7, 7.0 Hz,2H), 2.02 (d, J = 15.3 ¹³C NMR (101 MHz, CDCl₃) δ 171.32, 170.76 (d, J =7.1 Hz), 148.80 (s), 148.57 (s), 140.58 (s), 140.19 (d, J = 16.2 Hz),135.69 (s), Hz, 3H), 1.14 (dt, J = 9.2, 126.94 (s), 7.2 Hz, 3H) 126.33(t, J = 9.9 Hz), 124.09 (d, J = 12.2 Hz), 123.73 (s), 47.09 (s), 44.53(s), 44.01 (d, J = 46.2 Hz), 37.04 (s), 32.82 (m), 21.91 (s), 21.17 (s),13.05 (d, J = 3.3 Hz) F65

Brown Solid HRMS-ESI [M + H]⁺ calcd for C₁₇H₁₈ClF₃N₅O₂, 416.1096; found,416.1105 (400 MHz, CDCl₃) δ 8.94 (d, J = 2.7 Hz, 1H), 8.64 (dd, J = 4.7,1.4 Hz, 1H), 8.04 (ddd, J = 8.3, 2.7, 1.4 Hz, 1H), 7.95 (s, 1H), 7.47(dd, J = 8.4, 4.8 Hz, 1H), 6.80- 6.67 (multiple peaks, 2H), 6.46 (dt, J= 15.4, 2.0 Hz, 1H), 3.71 (q, J = 7.2 Hz, ¹⁹F NMR (376 MHz, CDCl₃) δ−65.02 IR (thin film) 3310, 3082, 1651 cm⁻¹ 2H), 3.61 (q, J = 5.9 Hz,2H), 2.50-2.33 (m, 2H), 1.17 (t, J = 7.2 Hz, 3H) F66

Colorless Oil ESIMS 418 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.97 (d, J = 2.4Hz, 1H), 8.61 (dd, J = 4.8, 1.4 Hz, 1H), 8.06 (s, 1H), 8.01 (ddd, J =8.3, 2.7, 1.5 Hz, 1H), 7.43 (ddd, J = 8.3, 4.8, 0.6 Hz, 1H), 5.31 (s,1H), 3.69 (s, 2H), 3.16 (m, 2H), 3.03 (s, 3H), 1.27 (d, J = 7.1 Hz, 3H),1.15 (t, J = 7.2 Hz, 3H) IR (thin film) 3096, 2979, 2939, 1657 cm⁻¹ F67

White Solid HRMS-ESI [M + H]⁺ calcd for C₁₆H₁₈ClF₃N₅O₂, 404.1096; found,404.1099 (400 MHz, CDCl₃) δ 8.96 (dd, J = 2.7, 0.7 Hz, 1H), 8.63 (dd, J= 4.8, 1.5 Hz, 1H), 8.08-7.95 (m, 2H), 7.46 (ddd, J = 8.3, 4.7, 0.7 Hz,1H), 6.56-6.37 (m, 1H), 3.90 (qd, J = 9.1, 6.5 Hz, 2H), 3.70 (q, J = 7.2Hz, 2H), 2.63-2.43 (m, 4H), 1.16 (t, J = 7.2 Hz, 3H) ¹⁹F NMR (376 MHz,CDCl₃) δ −72.57 IR (thin film) 3309, 3090, 1656 cm⁻¹ F68

Viscous Slightly cloudy Oil HRMS-ESI [M + H]⁺ calcd for C21H22Cl2N5O2,446.1145; found, 446.1148 (400 MHz, CDCl₃) δ 8.96 (dd, J = 2.7, 0.8 Hz,1H), 8.62 (dd, J = 4.8, 1.5 Hz, 1H), 8.06-7.99 (multiple peaks, 2H),7.45 (ddd, J = 8.4, 4.8, 0.8 Hz, 1H), 7.35- 7.12 (multiple peaks, 4H),6.39-6.26 (m, 1H), 4.41 (d, J = 6.0 Hz, 2H), 3.70 (q, J = 7.1 Hz, 2H),2.54 (br s, 4H), 1.14 (t, J = 7.2 Hz, 3H) IR (thin film) 3308, 3086 1653cm⁻¹ F69

Colorless Semi-Solid ESIMS 364.1 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.98 (d,J = 2.6 Hz, 1H), 8.62 (dd, J = 4.7, 1.3 Hz, 1H), 8.07- 8.01 (m, 2H),7.46 (ddd, J = 8.4, 4.8, 0.5 Hz, 1H), 4.35- 4.26 (m, 2H), 3.73-3.64 (m,4H), 3.52 (t, J = 6.5 Hz, 2H), 2.49 (t, J = 6.5 Hz, 2H), 1.16 (t, J =7.2 Hz, 3H) IR (thin film) 1735, 1657 cm⁻¹ F70

White Semi- Solid ESIMS 364.1 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.98 (d, J =2.6 Hz, 1H), 8.62 (dd, J = 4.7, 1.3 Hz, 1H), 8.07- 8.01 (m, 2H), 7.46(ddd, J = 8.4, 4.8, 0.5 Hz, 1H), 4.35- 4.26 (m, 2H), 3.73-3.64 (m, 4H),3.52 (t, J = 6.5 Hz, 2H), 2.49 (t, J = 6.5 Hz, 2H), 1.16 (t, J = 7.2 Hz,3H) IR (thin film) 3321, 3082, 1652 cm⁻¹ F71

Off White Solid 157° C. ESIMS 334 ([M + H]⁺) (300 MHz, CDCl₃) δ 8.95 (d,J = 2.4 Hz, 1H), 8.63 (d, J = 4.5 Hz, 1H), 8.05 (ddd, J = 8.4 Hz, 2.7Hz, 1.2 Hz, 1H), 7.99 (s, 1H), 7.47 (dd, J = 8.4 Hz, 4.8 Hz, 1H), 5.65(s, 1H), 3.74-3.60 (m, 4H), 3.15 (d, J = 3.3 Hz, 1H), 2.72 (dd, J = 17.1Hz, 3.9 Hz, 1H), 2.49-2.40 (m, 1H), 1.16 (t, J = 7.2 Hz, 3H) F72

Brown Oil ESIMS 426.3 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.96 (dd, J = 7.5,2.7 Hz, 1H), 8.62 (dd, J = 4.8, 1.4 Hz, 1H), 8.11-7.98 (m, 1H), 7.94 (d,J = 3.9 Hz, 1H), 7.45 (dd, J = 8.3, 4.8 Hz, 1H), 4.07-3.98 (m, 2H), 3.70(q, J = 7.1 Hz, 2H), 2.50 (d, J = 7.3 Hz, 2H), 2.39 (dd, J = 8.1, 6.3Hz, 2H), 1.94-1.84 (m, 1H), 1.82 (s, 3H), 1.41 (tdd, J = 11.8, 7.8, 4.3Hz, 1H), 1.19-1.10 IR (thin film) 3093, 2973, 2932, 1661 cm⁻¹ (m, 3H),1.09 (dt, J = 7.7, 4.3 Hz, 1H) F73

Clear Foam HRMS-ESI [M + H] calcd for C₁₇H₂₀ClF₃N₅O₂, 418.1252; found,418.1257 (400 MHz, CDCl₃) δ 8.96 (d, J = 2.6 Hz, 1H), 8.63 (dd, J = 4.8,1.5 Hz, 1H), 8.08- 7.99 (m, 2H), 7.46 (ddd, J = 8.3, 4.8, 0.7 Hz, 1H),6.25 (s, 1H), 3.70 (q, J = 7.2 Hz, 2H), 3.49 (q, J = 6.4 Hz, 2H), 2.49(s, 4H), 2.34 (qt, J = 10.8, 6.6 Hz, 2H), 1.15 ¹⁹F NMR (376 MHz, CDCl₃)δ −65.13 IR (thin film) 3319, 1656 cm⁻¹ (t, J = 7.2 Hz, 3H) F74

Light Yellow Gum ESIMS 438 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.98 (d, J =2.4 Hz, 1H), 8.61 (dd, J = 4.8 Hz, 1.2 Hz, 1H), 8.05 (ddd, J = 8.4 Hz,2.8 Hz, 1.2 Hz, 1H), 8.02 (s, 1H), 7.44 (dd, J = 8.4 Hz, 4.8 Hz, 1H),3.75-3.59 (m, 3H), 3.45-3.35 (m, 1H), 3.20-3.17 (m, 1H), IR (KBr): 3093,2924, 2852, 1743, 1668, 1442, 1120 cm⁻¹ 2.98-2.89 (m, 2H), 2.40-2.31 (m,2H), 2.10-2.06 (m, 1H), 2.01-1.92 (m, 1H), 1.72-1.64 (m, 1H), 1.51-1.46(m, 1H), 1.15 (t, J = 7.2 Hz, 3H), 1.11-1.05 (m, 1H) F75

White Hard Sticky Foam HRMS-ESI [M + H]⁺ calcd for C₁₈H₂₃ClN₅O₂,376.1535; found, 376.1534 (400 MHz, CDCl₃) δ 8.95 (d, J = 2.7 Hz, 1H),8.63 (dd, J = 4.7, 1.4 Hz, 1H), 8.04 (ddd, J = 8.3, 2.8, 1.5 Hz, 1H),7.96 (s, 1H), 7.46 (dd, J = 8.4, 4.7 Hz, 1H), 6.72 (t, J = 5.6 Hz,1H),3.71 (q, J = 7.2 Hz, 2H), 3.53 (q, J = 5.9 Hz, 2H), 2.37 (t, J = 5.7Hz, 2H), 2.12 (d, J = 7.1 Hz, IR (thin film) 3310, 3080, 1654 cm⁻¹ 2H),1.17 (t, J = 7.2 Hz, 3H), 1.02-0.85 (m, 1H), 0.66-0.53 (m, 2H),0.23-0.12 (m, 2H) F76

White Semi Solid ESIMS 320 ([M − BOC]⁺) ¹H NMR (400 MHz, CDCl₃) δ 8.95(br, 1H), 8.63 (dd, J = 5.1 Hz, 1H), 8.17-7.88 (m, 2H), 7.54- 7.36 (m,1H), 3.99-3.41 (m, 4H), 2.97-2.82 (m, 3H), 1.44 (s, 9H), 1.12 -0.83 (m,1H), 0.59-0.39 (m, 2H), 0.28-0.08 (m, 2H) IR (thin film) 1675 cm⁻¹ F77

Off-White Solid 133-136° C. ESIMS 348.1 ([M + H]⁺) (400 MHz, CDCl₃) δ8.98 (d, J = 2.6 Hz, 1H), 8.62 (dd, J = 4.7, 1.3 Hz, 1H), 8.19 (s, 1H),8.01 (ddd, J = 8.4, 2.7, 1.4 Hz, 1H), 7.50-7.38 (m, 1H), 3.97 (s, 2H),3.41 (d, J = 5.5 Hz, 2H), 3.25 (s, 3H), 2.38 (dd, J = 13.1, 6.8 Hz, 2H),1.85 (dd, J = 6.5, 3.3 Hz, 4H) IR (thin film) 1678, 1626 cm⁻¹ F78

White Semi- Solid HRMS-ESI [M + H]⁺ calcd for C₁₆H₂₁ClN₅O₃, 366.1327;found, 366.1335 (400 MHz, CDCl₃) δ 8.97 (dd, J = 2.7, 0.7 Hz, 1H), 8.61(dd, J = 4.7, 1.4 Hz, 1H), 8.08 (s, 1H), 8.03 (ddd, J = 8.3, 2.7, 1.5Hz, 1H), 7.45 (ddd, J = 8.4, 4.8, 0.8 Hz, 1H), 3.74 (s, 3H), 3.70 (q, J= 7.2 Hz, 2H), 3.17 (s, 3H), 2.78 (s, 2H), 2.46 (t, J = 6.6 Hz, 2H),1.16 (t, IR (thin film) 1661 cm⁻¹ J = 7.2 Hz, 3H) F79

Yellow Oil ESIMS 396 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.98 (d, J = 2.3 Hz,1H), 8.61 (d, J = 3.9 Hz, 1H), 8.05 (d, J = 7.8 Hz, 1H), 7.96 (s, 1H),7.44 (dd, J = 8.3, 4.7 Hz, 1H), 5.20 (s, 1H), 3.70 (s, 2H), 2.91 (s,3H), 2.63 (ddd, J = 20.3, 13.1, 6.8 Hz, 2H), 1.27 (d, J = 6.9 Hz, 3H),1.16 (t, J = 7.1 Hz, 3H), 1.10 (t, J = 7.4 Hz, 3H) IR (KBr thin film)3096, 2974, 2932, 1640 cm⁻¹ F80

White Solid HRMS-ESI [M + H]⁺ calcd for C₂₁H₂₂ClFN₅O₂, 430.1441; found,430.1446 (400 MHz, CDCl₃) δ 9.01- 8.93 (m, 1H), 8.62 (dd, J = 4.7, 1.5Hz, 1H), 8.03 (ddd, J = 8.3, 2.7, 1.4 Hz, 1H), 8.00 (s, 1H), 7.45 (ddd,J = 8.4, 4.8, 0.8 Hz, 1H), 7.25 (dd, J = 8.1, 5.0 Hz, 2H), 7.06-6.97 (m,2H), 6.21-6.14 (m, 1H), 4.43-4.34 (m, 2H), 3.70 (q, J = 7.1 Hz, 2H),2.52 (s, 4H), 1.15 (t, J = 7.2 Hz, 3H) ¹⁹F NMR (376 MHz, CDCl₃) δ−115.23 IR (thin film) 3309, 3085, 1654 cm⁻¹ F81

Light Yellow Gum ESIMS 390 ([M + H]⁺) (400 MHz, CDCl₃) δ 9.02 (d, J =2.4 Hz, 1H), 8.64 (d, J = 4.0 Hz, 1H), 8.11-8.08 (m, 1H), 8.04 (s, 1H),7.48 (dd, J = 8.4 Hz, 4.8 Hz, 1H), 3.71 (q, J = 7.2 Hz, 2H), 3.33 (t, J= 5.2 Hz, 1H), 3.22 (q, J = 7.2 Hz, 2H), 3.09- 3.06 (m, 1H), 2.94 (dd, J= 5.6 Hz, 2.4 Hz, 1H) 2.22 (t, J = 6.4 Hz, 2H), 1.75-1.72 IR (KBr):3089, 2931, 1732, 1666, 1585, 1440, 1259 cm⁻¹ (m, 4H), 1.17 (t, J = 7.2Hz, 3H), 1.14 (t, J = 7.2 Hz, 3H) F82

Off-White Solid 135° C. ESIMS 416.2 ([M + H]⁺) ¹H NMR (400 MHz, CDCl₃) δ8.96 (d, J = 2.5 Hz, 1H), 8.61 (dd, J = 4.7, 1.3 Hz, 1H), 8.12 (s, 1H),8.04 (ddd, J = 8.3, 2.7, 1.4 Hz, 1H), 7.44 (ddd, J = 8.4, 4.8, 0.5 Hz,1H), 3.63-3.48 (m, 4H), 3.48-3.34 (m, 2H), 2.58 (d, J = 63.8 Hz, 4H),1.57 (ddd, J = 22.6, 10.8, 5.1 Hz, 6H), 1.05-0.80 (m, 1H), 0.53-0.40 (m,2H), 0.17 (q, J = 4.7 Hz, 2H) IR (thin film) 1630 cm⁻¹ F83

White Solid HRMS-ESI [M + H]⁺ calcd for C₂₀H₂₁ClN₅O₂, 398.1378; found,398.1379 (400 MHz, CDCl₃) δ 9.00 (d, J = 2.7 Hz, 0.75H, major), 8.80 (s,0.25H, minor), 8.63 (dd, J = 4.8, 1.5 Hz, 1H), 8.17 (s, 0.75H, major),8.03 (dt, J = 8.1, 2.3 Hz, 0.75H, major), 7.95 (d, J = 8.6 Hz, 0.25H,minor), 7.54-7.33 (multiple peaks, 6H), 7.50 (s, 0.25H, minor), 4.10 (brs, 1.5H), 3.88-3.71 (m, 2H), 3.68 (br s, 0.5H, IR (thin film) 3087,1680, 1631 cm⁻¹ minor), 3.15 (s, 0.75H, minor), 3.08 (s, 2.25H, major),1.20 (t, J = 7.2, 2.25H, major), 1.14 (t, J = 7.2 Hz, 0.75H, minor) F84

Light Green Gum ESIMS 362 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.95 (s, 1H),8.63 (d, J = 4.0 Hz, 1H), 8.05-8.02 (m, 1H), 7.99 (s, 1H), 7.46 (dd, J =4.8 Hz, 8.4 Hz, 1H), 3.69 (q, J = 7.2 Hz, 2H), 3.54-3.47 (m, 2H), 3.21(q, J = 7.2 Hz, 2H), 3.06 (dd, J = 5.6 Hz, 1.6 Hz, 1H), 2.72 (dd, J =16.8 Hz, 4.0 Hz, 1H), 2.40-2.34 (m, 1H), 1.17-1.12 (m, 6H) IR (KBr):3437, 2929, 2852, 1735, 1666, 1440, 1255 cm⁻¹ F85

Light Brown Viscous Semi-Solid HRMS-ESI [M + H]⁺ calcd forC₁₇H₂₀ClF₃N₅O₂, 418.1252; found, 418.1269 (400 MHz, CDCl₃) δ 9.01- 8.93(m, 1H), 8.62 (dd, J = 4.8, 1.4 Hz, 1H), 8.09 (d, J = 5.0 Hz, 1H),8.07-8.00 (m, 1H), 7.45 (ddt, J = 8.3, 4.8, 0.9 Hz, 1H), 4.11-3.91 (m,2H), 3.70 (q, J = 7.1 Hz, 2H), 3.17 (s, 2.3H), 3.03 (s, 0.7H), 2.70 (brd, J = 16.9 Hz, 2H), 2.51 (s, 2H), 1.15 (t, J = 7.2 Hz, 3H) ¹⁹F NMR (376MHz, CDCl₃) δ −70.02 (major rotamer), −70.45 (minor rotamer) IR (thinfilm) 3093, 1600 cm⁻¹ F86

Orange oil ESIMS 361 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.97 (d, J = 2.6 Hz,1H), 8.63 (dd, J = 4.8, 1.4 Hz, 1H), 8.12 (s, 1H), 8.07 (ddd, J = 8.3,2.7, 1.5 Hz, 1H), 7.48 (dd, J = 8.3, 4.8 Hz, 1H), 6.74 (d, J = 9.0 Hz,1H), 5.91 (dt, J = 5.5, 2.2 Hz, 1H), 5.73 (ddd, J = 5.5, 2.5, 1.1 Hz,1H), 5.05 (dddd, J = 9.6, 7.0, 3.4, IR (thin film) 3287, 3066 2937, 16501587, 1534 cm⁻¹ 1.7 Hz, 1H), 3.57 (dq, J = 8.3, 2.3 Hz, 1H), 3.26 (s,3H), 2.25 (dt, J = 13.8, 8.3 Hz, 1H), 1.99 (s, 3H), 1.87 (dt, J = 13.8,2.3 Hz, 1H) F87

Light Brown Gum ESIMS 521 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.98 (d, J = 2.4Hz, 1H), 8.62 (d, J = 3.6 Hz, 1H), 8.60 (s, 1H), 8.06 (ddd, J = 8.4 Hz,2.4 Hz, 1.6 Hz, 1H), 7.99 (s, 1H), 7.77-7.75 (m, 1H), 7.68 (d, J = 8.0Hz, 1H), 7.46 (dd, J = 8.4 Hz, 4.8 Hz, 1H), 4.44 (s, 2H), 3.69 (q, J =14.4 Hz, IR (KBr): 3093, 2935, 1743, 1664, 1558, 1440, 1156 cm⁻¹ 7.2 Hz,2H), 3.31 (t, J = 5.2 Hz, 1H), 3.20-3.19 (m, 1H), 2.92 (dd, J = 5.2 Hz,2.0 Hz, 1H), 2.19 (t, J = 6.8 Hz, 2H), 1.73-1.65 (m, 4H), 1.15 (t, J =7.2 Hz, 3H) F88

Colorless Oil ESIMS 380.1 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.99 (d, J = 2.5Hz, 1H), 8.62 (dd, J = 4.7, 1.4 Hz, 1H), 8.13- 7.97 (m, 2H), 7.46 (ddd,J = 8.3, 4.8, 0.6 Hz, 1H), 3.76 (t, J = 7.3 Hz, 2H), 3.70 (dd, J = 14.0,7.0 Hz, 2H), 3.57 (t, J = 6.5 Hz, 2H), 3.25 (t, J = 7.3 Hz, 2H), 2.47(t, J = 6.5 Hz, 2H), 1.16 (t, J = 7.2 Hz, 3H) IR (thin film) 1653 cm⁻¹F89

Light Brown Oil ESIMS 482.2 ([M +H]⁺) (400 MHz, CDCl₃) δ 8.96 (t, J =2.4 Hz, 1H), 8.70- 8.53 (m, 1H), 8.04 (ddd, J = 8.3, 2.7, 1.5 Hz, 1H),7.96 (d, J = 9.9 Hz, 1H), 7.50- 7.40 (m, 1H), 6.13-5.72 (m, 1H), 3.87(td, J = 14.5, 3.6 Hz, 1H), 3.81-3.63 (m, 4H), 3.63-3.49 (m, 1H),2.75-2.67 (m, 1H), 2.62-2.33 (m, 5H), IR (thin film) 3094, 2976, 1650cm⁻¹ 1.17 (t, J = 6.9 Hz, 3H) F90

Yellow Semi- Solid (400 MHz, CDCl₃) δ 8.95 (d, J = 2.5 Hz, 1H), 8.62 (d,J = 4.8 Hz, 1H), 8.14-7.84 (m, 2H), 7.59-7.35 (m, 1H). 3.94-3.72 (d, J =25.9 Hz, 2H), 3.31-3.15 (m, 3H), 2.99-2.81 (m, 3H), 1.53- 1.31 (s, 9H)F91

Light Yellow Gum ESIMS 507 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.98 (s, 1H),8.62 (d, J = 3.6 Hz, 1H), 8.59 (s, 1H), 8.07-8.04 (m, 2H), 7.76-7.67 (m,2H), 7.44 (dd, J = 8.4 Hz, 4.8 Hz, 1H), 4.49-4.36 (m, 2H), 3.74-3.64 (m,2H), 3.34-3.25 (m, 2H), 2.91 (dd, J = 5.2 Hz, 2.0 Hz, 1H), 2.38-2.35 (m,2H), 2.11-1.98 (m, 2H), IR (KBr): 3446, 2924, 1743, 1664, 1585, 1440,1336, 1136 cm⁻¹ 1.15 (t, J = 7.2 Hz, 3H) F92

Colorless Oil ESIMS 350 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.96 (d, J = 2.3Hz, 1H), 8.62 (m, 1H), 8.06 (ddt, J = 8.3, 2.7, 1.4 Hz, 1H), 7.98 (d, J= 11.0 Hz, 1H), 7.47 (ddd, J = 8.3, 4.8, 0.5 Hz, 1H), 3.78 (s, 2H), 3.71(m, 3H), 2.51 (d, J = 7.6 Hz, 2H), 2.38 (d, J = 7.7 Hz, 2H), 1.80 (s,3H), 1.16 (t, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 172.14 (s),156.21 (s), 148.61 (s), 141.00 (s), 139.98 (s), 135.69 (s), 126.30 (s),124.16 (d, J = Mixture of E and Z isomer 7.6 Hz), 61.15 in 3:1 ratio,major isomer (d, J = 7.9 Hz), reported 43.83 (s), 31.20 (s), 30.11 (d, J= 13.4 Hz), 25.40 (s), 20.39 (s), 14.69 (s), 13.13 (s) F93

Light Yellow Oil ESIMS 367 ([M + H]⁺) ¹H NMR (400 MHz, CDCl₃) δ 9.00 (d,J = 2.5 Hz, 1H), 8.61 (dd, J = 4.7, 1.2 Hz, 1H), 8.25 (s, 1H), 8.03(ddd, J = 8.3, 2.6, 1.4 Hz, 1H), 7.44 (dd, J = 8.3, 4.8 Hz, 1H), 4.98(q, J = 6.7 Hz, 1H), 3.70 (m, 2H), 2.96 (s, 3H), 2.88 (s, 3H), 1.36 (d,J = 6.8 Hz, 3H), 1.17 (t, J = 7.2 Hz, 3H) F94

Viscous Clear Oil HRMS-ESI [M + H]⁺ calcd for C₁₈H₂₂ClF₃N₅O₂, 432.1409;found, 432.1417 (400 MHz, CDCl₃) δ 9.03- 8.95 (m, 1H), 8.63 (ddd, J =7.2, 4.7, 1.5 Hz, 1H), 8.10- 7.90 (multiple peaks, 2H), 7.46 (tdd, J =8.3, 4.8, 0.7 Hz, 1H), 3.77-3.54 (multiple peaks, 4H), 3.06 (s, 2.2H,major), 2.84 (s, 0.8H, minor), 2.66-2.32 (multiple peaks, 6H), 1.16 (dt,J = ¹⁹F NMR (376 MHz, CDCl₃) δ −66.52 (minor rotamer), −66.60 (majorrotamer) IR (thin film) 3500, 3092, 1648 cm⁻¹ 8.7, 7.2 Hz, 3H) F95

White Semi- Solid ESIMS 402.0 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.97 (d, J =2.5 Hz, 1H), 8.61 (dd, J = 4.7, 1.4 Hz, 1H), 8.14 (s, 1H), 8.04 (ddd, J= 8.3, 2.7, 1.5 Hz, 1H), 7.50-7.38 (m, 1H), 3.62-3.36 (m, 6H), 2.65-2.42(m, 4H), 1.95 (p, J = 6.8 Hz, 2H), 1.84 (p, J = 6.6 Hz, 2H), 1.02-0.90(m, 1H), 0.53-0.42 (m, 2H), 0.24-0.10 (m, 2H) IR (thin film) 1625 cm⁻¹F96

Yellow Oil (400 MHz, CDCl₃) δ 8.99 (d, J = 2.5 Hz, 1H), 8.60 (dd, J =4.8, 1.4 Hz, 1H), 8.10 (s, 1H), 8.02 (ddd, J = 8.3, 2.7, 1.5 Hz, 1H),7.43 (ddd, J = 8.3, 4.8, 0.6 Hz, 1H), 3.70 (s, 2H), 3.01 (s, 3H), 1.99(s, 3H), 1.76 (s, 1H), 1.25 (d, J = 7.1 Hz, 3H), 1.15 (t, J = 7.2 Hz,3H) IR (KBr thin film) 3093, 2978, 2934, 1632 cm⁻¹ F97

Off-White Solid HRMS-ESI [M + H]⁺ calcd for C16H₁₈ClF₃N₅O₂, 404.1096;found, 404.1108 (400 MHz, CDCl₃) δ 8.97- 8.90 (m, 1H), 8.65 (dd, J =4.8, 1.4 Hz, 1H), 8.05 (ddd, J = 8.4, 2.7, 1.5 Hz, 1H), 7.99 (s, 1H),7.48 (ddd, J = 8.4, 4.8, 0.8 Hz, 1H), 6.46 (br s, 1H), 3.85 (d, J = 4.2Hz, 2H), 3.74 (q, J = 7.2 Hz, 2H), 2.59-2.36 (multiple peaks, 4H), 1.19(t, J = 7.2 Hz, 3H) ¹⁹F NMR (376 MHz, CDCl₃) δ −66.83 IR (thin film)3332, 3088, 1653 cm⁻¹ F98

White Semi- Solid ESIMS 374 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.98 (d, J =2.5 Hz, 1H), 8.70- 8.57 (m, 1H), 8.12 (s, 1H), 8.03 (ddd, J = 8.3, 2.7,1.4 Hz, 1H), 7.46 (dd, J = 8.3, 4.8 Hz, 1H), 4.10-3.68 (m, 2H),3.65-3.37 (m, 4H), 2.40 (t, J = 8.1 Hz, 2H), 2.18-1.95 (m, 2H), 1.04-0.92 (m, 1H), 0.58-0.42 (m, 2H), 0.26-0.11 (m, 2H) IR (thin film) 1666cm⁻¹ F99

Orange Solid HRMS-ESI [M + H]⁺ calcd for C₁₆H₁₆ClF₃N₅O₂, 402.0939;found, 402.0953 (400 MHz, CDCl₃) δ 8.95 (dd, J = 2.7, 0.7 Hz, 1H), 8.66(dd, J = 4.8, 1.4 Hz, 1H), 8.06 (ddd, J = 8.3, 2.7, 1.5 Hz, 1H), 8.01(s, 1H), 7.48 (ddd, J = 8.3, 4.8, 0.8 Hz, 1H), 6.82-6.68 (multiplepeaks, 2H), 6.56 (dq, J = 15.4, 1.9 Hz, 1H), 3.94 (d, J = 4.3 Hz, 2H),3.76 (q, J = 7.2 Hz, 2H), 1.20 (t, J = 7.2 ¹⁹F NMR (376 MHz, CDCl₃) δ−65.10 IR (thin film) 3317, 3086, 1648 cm⁻¹ Hz, 3H) F100

Off-White Solid 104-106° C. ESIMS 404.2 ([M + H]⁺) (400 MHz, CDCl₃) δ8.97 (d, J = 2.6 Hz, 1H), 8.61 (dd, J = 4.7, 1.4 Hz, 1H), 8.13 (s, 1H),8.03 (ddd, J = 8.4, 2.7, 1.4 Hz, 1H), 7.44 (ddd, J = 8.3, 4.8, 0.6 Hz,1H), 3.71 (q, J = 7.2 Hz, 2H), 3.53- 3.43 (m, 4H), 2.66 (d, J = 5.7 Hz,2H), 2.50 (d, J = 5.8 Hz, 2H), 1.74-1.63 (m, 4H), 1.62-1.49 (m, 4H),1.15 (t, J = 7.2 Hz, 3H) IR (thin film) 1625 cm⁻¹ F101

Light Yellow Solid HRMS-ESI [M + H]⁺ calcd for C₁₆H₁₈ClN₆O₂, 361.1174;found, 361.1178 (400 MHz, CDCl₃) δ 8.95 (d, J = 2.7 Hz, 1H), 8.64 (dd, J= 4.8, 1.5 Hz, 1H), 8.04 (ddd, J = 8.3, 2.7, 1.4 Hz, 1H), 7.97 (s, 1H),7.47 (dd, J = 8.4, 4.8 Hz, 1H), 6.93 (br s, 1H), 3.72 (q, J = 7.3 Hz,2H), 3.56 (q, J = 5.8 Hz, 2H), 3.33 (s, 2H), 2.39 (t, J = 5.7 Hz, 2H),1.18 (t, J = IR (thin film) 3313, 3093, 2254, 1660 cm⁻¹ 7.2 Hz, 3H) F102

White Semi- Solid HRMS-ESI [M + H]⁺ calcd for C₁₆H₁₈ClN₆O₂, 361.1174;found, 361.1178 (400 MHz, CDCl₃) δ 8.95 (d, J = 2.7 Hz, 1H), 8.64 (dd, J= 4.8, 1.5 Hz, 1H), 8.04 (ddd, J = 8.3, 2.7, 1.4 Hz, 1H), 7.97 (s, 1H),7.47 (dd, J = 8.4, 4.8 Hz, 1H), 6.93 (br s, 1H), 3.72 (q, J = 7.3 Hz,2H), 3.56 (q, J = 5.8 Hz, 2H), 3.33 (s, 2H), 2.39 (t, J = 5.7 Hz, 2H),1.18 (t, J = IR (thin film) 3525, 3094, 1656 cm⁻¹ 7.2 Hz, 3H) F103

Light Green Gum ESIMS 376 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.98 (d, J = 2.4Hz, 1H), 8.61 (d, J = 4.4 Hz, 1H), 8.06-8.04 (m, 2H), 7.45 (dd, J = 8.4Hz, 4.8 Hz, 1H), 3.78-3.63 (m, 2H), 3.32 (t, J = 5.2 Hz, 1H), 3.24-3.10(m, 3H), 2.90 (dd, J = 5.2 Hz, 2.0 Hz, 1H), 2.42-2.30 (m, 2H), 2.13-2.04IR (KBr): 3089, 2972, 2358, 1735, 1649, 1440, 1355, 1246 cm⁻¹ (m, 1H),1.98-1.89 (m, 1H), 1.15 (t, J = 7.2 Hz, 3H), 1.09 (t, J = 7.2 Hz, 3H)F104

Light Yellow Gum ESIMS 452 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.99 (d, J =7.6 Hz, 1H), 8.63 (bs, 1H), 8.07 (d, J = 8.4 Hz, 1H), 7.99 (d, J = 1.2Hz, 1H), 7.46 (bs, 1H), 3.72- 3.60 (m, 3H), 3.59-3.33 (m, 1H),3.13-3.12. (m, 1H), 3.04-2.94 (m, 2H), 2.20 (t, J = 6.8 Hz, 2H),1.73-1.63 (m, 4H), 1.52-1.50 (m, 2H), IR (KBr): 3441, 2924, 2852, 1741,1664, 1440, 1390 cm⁻¹ 1.15 (t, J = 7.2 Hz, 3H), 1.11-1.07 (m, 1H) F105

Colorless Gum ESIMS 336.2 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.95 (d, J = 2.6Hz, 1H), 8.61 (dt, J = 4.9, 1.3 Hz, 1H), 8.05 (ddt, J = 8.3, 2.8, 1.4Hz, 1H), 7.98-7.96 (s, 1H), 7.45 (ddd, J = 8.3, 4.8, 0.8 Hz, 1H),3.76-3.65 (m, 2H), 2.62 (dd, J = 8.2, 7.1 Hz, 1H), 2.53 (dd, J = 8.2,6.3 Hz, 1H), 2.37 (dd, J = 8.2, 6.5 Hz, 2H), 1.84 (s, 3H), 1.18- 1.11(m, 3H). One proton not located F106

White Semi- Solid ESIMS 376.2 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.98 (d, J =2.6 Hz, 1H), 8.61 (dd, J = 4.7, 1.4 Hz, 1H), 8.14 (s, 1H), 8.03 (ddd, J= 8.3, 2.7, 1.5 Hz, 1H), 7.44 (ddd, J = 8.4, 4.8, 0.6 Hz, 1H), 3.71 (q,J = 7.1 Hz, 2H), 3.51- 3.38 (m, 4H), 2.58 (dd, J = 32.2, 26.5 Hz, 4H),2.01- 1.90 (m, 2H), 1.90-1.79 (m, 2H), 1.15 (t, J = 7.2 Hz, 3H) IR (thinfilm) 1625 cm⁻¹ F107

Colorless Semi-Solid ESIMS 348.1 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.98 (d,J = 2.5 Hz, 1H), 8.62 (dd, J = 4.7, 1.4 Hz, 1H), 8.13 (s, 1H), 8.05(ddd, J = 8.3, 2.7, 1.5 Hz, 1H), 7.45 (ddd, J = 8.3, 4.8, 0.5 Hz, 1H),3.54 (t, J = 6.9 Hz, 2H), 3.46 (t, J = 7.1 Hz, 2H), 3.23 (s, 3H), 2.47(t, J = 6.9 Hz, 2H), 2.33 (t, J = 8.1 Hz, 2H), 2.07-1.91 (m, 2H) IR(thin film) 1656 cm⁻¹ F108

Clear Viscous Oil HRMS-ESI [M + H]⁺ calcd for C₁₈H₂₂ClF₃N₅O₂, 432.1409;found, 432.1411 (400 MHz, CDCl₃) δ 8.97 (dd, J = 2.7, 0.6 Hz, 1H), 8.61(dd, J = 4.8, 1.4 Hz, 1H), 8.10 (d, J = 1.8 Hz, 1H), 8.03 (ddd, J = 8.4,2.7, 1.4 Hz, 1H), 7.45 (ddd, J = 8.3, 4.8, 0.8 Hz, 1H), 3.70 (q, J = 7.1Hz, 1.53H), 3.66- 3.59 (m, 0.47H), 3.59-3.52 ¹⁹F NMR (376 MHz, CDCl₃) δ−65.34 (major rotamer), −65.39 (minor rotamer) IR (thin film) 3368, (m,2H), 3.07 (s, 2.3H), 2.93 1641 cm⁻¹ (s, 0.7H), 2.64 (s, 2H), 2.56- 2.44(m, 2H), 2.35 (qt, J = 10.8, 7.2 Hz, 2H), 1.17-1.10 (m, 3H) F109

White Solid ESIMS 418 ([M + H]⁺) 416 ([M − H]⁻) (400 MHz, CDCl₃) δ 9.01-8.93 (d, J = 2.8 Hz, 1H), 8.66-8.60 (m, 1H), 8.11-8.02 (m, 2H),7.52-7.42 (m, 1H), 5.93-5.85 (m, 1H), 5.72- 5.66 (m, 1H), 5.53-5.44 (d,J = 9.5 Hz, 1H), 4.80-4.67 (m, 1H), 3.58-3.47 (m, 1H), 3.30-3.21 (s,3H), 2.35-2.22 (m, 1H), 1.90-1.80 (m, 1H), 1.51-1.34 (s, 9H) ¹³C NMR(101 MHz, CDCl₃) δ 175.26, 155.23, 148.70, 140.31, 140.00, 135.61,135.18, 130.99, 126.34, 125.92, 125.78, 124.12, 79.04, 55.69, 47.33,37.49, 35.55, 28.45 F110

White Semi- Solid ESIMS 334.2 ([M + H − OtBu]⁺) (400 MHz, CDCl₃) δ 8.97(d, J = 2.7 Hz, 1H), 8.63 (dd, J = 4.7, 1.5 Hz, 1H), 8.07 (ddd, J = 8.3,2.7, 1.4 Hz, 1H), 7.97 (s, 1H), 7.47 (ddd, J = 8.4, 4.7, 0.8 Hz, 1H),4.18-3.95 (m, 2H), 3.77- 3.59 (m, 2H), 2.66-2.47 (m, 2H), 2.37 (ddt, J =11.3, 8.1, 3.9 Hz, 1H), 1.80-1.66 (m, 2H), 1.64-1.54 (m, 2H), 1.44 IR(thin film) 1664 cm⁻¹ (s, 9H), 1.15 (t, J = 7.1 Hz, 3H) F111

White Solid 167-169° C. ESIMS 336.1 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.98(d, J = 2.5 Hz, 1H), 8.63 (dd, J = 4.7, 1.4 Hz, 1H), 8.14 (s, 1H), 8.03(ddd, J = 8.3, 2.7, 1.4 Hz, 1H), 7.50-7.38 (m, 1H), 4.43-4.34 (m, 2H),3.91 (s, 2H), 3.77 (t, J = 8.0 Hz, 2H), 3.26 (s, 3H) IR (thin film)1749, 1667 cm⁻¹ F112

White Foam HRMS-ESI [M + H]⁺ calcd for C₂₁H₂₈ClN₆O₃, 447.1906; found,447.1902 (400 MHz, CDCl₃) δ 8.95 (d, J = 2.7 Hz, 1H), 8.64 (dd, J = 4.8,1.5 Hz, 1H), 8.04 (ddd, J = 8.3, 2.7, 1.4 Hz, 1H), 7.96 (s, 1H),7.50-7.43 (m, 1H), 6.49 (t, J = 5.6 Hz, 1H), 4.59 (d, J = 13.6 Hz, 1H),3.85 (d, J = 13.7 Hz, IR (thin film) 3310, 3083, 1626, 1441 cm⁻¹ 1H),3.70 (q, J = 7.2 Hz, 2H), 3.55-3.43 (m, 2H), 3.08 (td, J = 13.6, 12.8,2.9 Hz, 1H), 2.70-2.56 (m, 1H), 2.38-2.23 (multiple peaks, 3H), 2.09 (s,3H), 1.86 (t, J = 13.4 Hz, 2H), 1.75-1.63 (m, 2H), 1.17 (t, J = 7.2 Hz,3H) F113

Yellow Viscous Oil HRMS-ESI [M + H]⁺ calcd for C₁₈H₂₁ClF₂N₅O₂, 412.1346;found, 412.1368 (400 MHz, CDCl₃) δ 8.94 (dd, J = 2.7, 0.8 Hz, 1H), 8.63(dd, J = 4.7, 1.4 Hz, 1H), 8.03 (ddd, J = 8.3, 2.7, 1.4 Hz, 1H), 7.93(s, 1H), 7.46 (ddd, J = 8.3, 4.8, 0.8 Hz, 1H), 6.75-6.63 (m, 1H),3.85-3.63 (m, 2H), 3.63-3.46 (m, 2H), 2.37 (qdd, J = 16.9, ¹⁹F NMR (376MHz, CDCl₃) δ −135.79 (d, J = 153.1 Hz), −153.4 Hz) IR (thin film) 3335,3091, 1658 cm⁻¹ 6.7, 4.5 Hz, 2H), 2.14 (ddd, J = 13.5, 7.9, 6.0 Hz, 1H),1.46 (t, J = 2.3 Hz, 3H), 1.28-1.21 (m, 1H), 1.17 (t, J = 7.2 Hz, 3H)F114

Orange Solid 130-131° C. ESIMS 379 ([M + H]⁺) (400 MHz, CDCl₃) δ 9.01(d, J = 2.5 Hz, 1H), 8.59 (dd, J = 4.8, 1.4 Hz, 1H), 8.25 (s, 1H), 8.03(ddd, J = 8.3, 2.7, 1.4 Hz, 1H), 7.42 (ddd, J = 8.3, 4.8, 0.6 Hz, 1H),4.45 (dd, J = 14.4, 7.3 Hz, 1H), 3.92 (m, 1H), 3.47 (dt, J = 11.7, 5.9Hz, 1H), 2.98 (s, 3H), 2.72 (s, 6H), 1.30 (d, J = 7.2 Hz, 3H), 1.16 (t,J = IR (thin film) 3311, 3079, 1656 cm⁻¹ 7.2 Hz, 3H) F115

Light Yellow Solid HRMS-ESI [M + H]⁺ calcd for C₂₀H₂₂ClN₆O₂, 413.1487;found, 413.1475 (400 MHz, CDCl₃) δ 8.96 (dd, J = 2.7, 0.7 Hz, 1H), 8.62(dd, J = 4.8, 1.5 Hz, 1H), 8.58-8.53 (m, 2H), 8.03 (ddd, J = 8.4, 2.7,1.5 Hz, 1H), 8.00 (s, 1H), 7.45 (ddd, J = 8.4, 4.8, 0.8 Hz, 1H),7.23-7.16 (m, 2H), 6.45-6.36 (m, 1H), 4.45 (d, J = 6.1 Hz, 2H), 3.71 (q,J = 7.2 Hz, 2H), 2.63-2.49 IR (thin film) 3311, 3079, 1656 cm⁻¹(multiple peaks, 4H), 1.16 (t, J = 7.2 Hz, 3H) F116

White Foam ESIMS 418 ([M + H]⁺) 416 ([M − H]⁻) (400 MHz, CDCl₃) δ 8.97(d, J = 2.7 Hz, 1H), 8.63 (dd, J = 4.4, 1.8 Hz, 1H), 8.11- 8.03 (m, 2H),7.47 (dd, J = 8.4, 4.7 Hz, 1H), 5.90 (dt, J = 4.4, 2.3 Hz, 1H), 5.73-5.65 (m, 1H), 5.48 (d, J = 9.1 Hz, 1H), 4.74 (t, J = 9.2 Hz, 1H), 3.53(dt, J = 7.9, 2.5 Hz, 1H), 3.25 (d, J = 1.7 Hz, 3H), 2.28 (dt, J = 13.5,¹³C NMR (101 MHz, CDCl₃) δ 175.24, 155.22, 148.62, 140.22, 139.97,135.58, 135.13, 131.01, 126.29, 126.09, 125.69, 124.09, 78.99, 55.67,47.31, 37.45, 35.54, 8.4 Hz, 1H), 1.86 (dd, J = 28.43 13.6, 2.7 Hz, 1H),1.44 (d, J = 1.7 Hz, 9H) F117

Light Yellow Gum ESIMS 493 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.96 (d, J =2.8 Hz, 1H), 8.64 (d, J = 3.6 Hz, 1H, 8.61 (s, 1H), 8.05 (ddd, J = 8.4Hz, 2.8 Hz, 1.2 Hz, 1H), 7.99 (s, 1H), 7.80 (d, J = 6.8 Hz, 1H), 7.68(d, J = 8.4 Hz, 1H), 7.47 (dd, J = 8.4 Hz, 4.8 Hz, 1H), 4.51-4.41 (m, IR(KBr): 3095, 2924, 1747, 1666, 1585, 1442, 1336, 1136 cm⁻¹ 2H),3.73-3.63 (m, 2H), 3.61-3.56 (m, 1H), 3.50 (t, J = 5.6 Hz, 1H), 3.10(dd, J = 5.6 Hz, 2.0 Hz, 1H), 3.10 (dd, J = 5.6 Hz, 2.0 Hz, 1H), 2.72(dd, J = 16.8 Hz, 4.0 Hz, 1H), 2.41 (dd, J = 16.8 Hz, 10.0 Hz, 1H), 1.14(t, J = 7.2 Hz, 3H) F118

Cloudy White Viscous Semi-Solid HRMS-ESI [M + H]⁺ calcd forC₂₂H₂₄ClFN₅O₂, 444.1597; found, 444.1602 (400 MHz, CDCl₃) δ 8.97 (d, J =2.7 Hz, 1H), 8.62 (dd, J = 4.8, 1.4 Hz, 1H), 8.11 (d, J = 1.8 Hz, 1H),8.07-8.00 (m, 1H), 7.48-7.42 (m, 1H), 7.18 (ddd, J = 8.3, 5.2, 2.5 Hz,2H), 7.09-6.94 (m, 2H), 4.54 (d, J = 5.3 Hz, 2H), 3.72 (q, J = 7.3 Hz,2H), 2.96 (s, 2H, major), 2.90 (s, 1H, minor), 2.79-2.63 (m, 2H),2.60-2.42 (m, 2H), ¹⁹F NMR (376 MHz, CDCl₃) δ −114.88 (minor rotamer),−115.46 (major rotamer) IR (thin film) 3082, 1646 cm⁻¹ 1.16 (td, J =7.2, 3.5 Hz, 3H) F119

Light Green Gum ESIMS 362 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.99 (d, J = 2.4Hz, 1H), 8.61 (d, J = 3.6 Hz, 1H), 8.07-8.05 (m, 2H), 7.45 (dd, J = 8.4Hz, 4.8 Hz, 1H), 3.76-3.62 (m, 2H), 3.33 (t, J = 5.2 Hz, 1H), 3.17-3.15(m, 1H), 2.91 (dd, J = 5.2 Hz, 2.0 Hz, 1H), 2.77 (s, 3H), 2.42-2.30 IR(KBr): 3473, 3089, 2926, 1732, 1716, 1427, 1247, 1114 cm⁻¹ (m, 2H),2.13-2.04 (m, 1H), 1.99-1.90 (m, 1H), 1.15 (t, J = 7.2 Hz, 3H) F120

White Solid HRMS-ESI [M + H]⁺ calcd for C₁₆H₁₈ClF₃N₅O₂, 404.1096; found,404.1096 (400 MHz, CDCl₃) δ 8.98 (d, J = 2.8 Hz, 1H), 8.63 (d, J = 5.1Hz, 1H), 8.09 (s, 1H), 8.02-7.96 (m, 1H), 7.46 (dd, J = 8.4, 4.8 Hz,1H), 3.99 (br s, 2H), 3.71 (q, J = 7.4 Hz, 2H), 3.27 (q, J = 9.9 Hz,2H), 3.15 (br s, 2.6H, major), 2.97 (s, 0.4H, minor), 1.17 (t, J = 7.2Hz, ¹⁹F NMR (376 MHz, CDCl₃) δ −62.48 (minor rotamer), −62.62 (majorrotamer) IR (thin film) 3533, 3095, 1663 cm⁻¹ 3H) F121

Light Yellow Oil ESIMS 379 ([M + H]⁺) (400 MHz, CDCl₃) δ 9.02 (d, J =2.4 Hz, 1H), 8.62 (dd, J = 4.7, 1.4 Hz, 1H), 8.11 (s, 1H), 8.09 (ddd, J= 8.3, 2.7, 1.5 Hz, 1H), 7.45 (ddd, J = 8.3, 4.8, 0.7 Hz, 1H), 3.69 (d,J = 7.1 Hz, 2H), 3.47 (m, 2H), 2.79 (s, 3H), 2.76 (s, 6H), 2.42 (t, J =7.1 Hz, 2H), 1.14 (t, J = 7.2 Hz, 3H) ¹³C NMR (101 MHz, CDCl₃) δ 171.62,165.01, 148.55, 140.59, 140.30, 135.73, 127.08, 126.37, 124.03, 123.80,46.62, 43.72, 38.65, 37.20, 32.23, 13.07 F122

White Semi- Solid (400 MHz, CDCl₃) δ 9.04 (s, 1H), 8.64 (d, J = 4.8 Hz,1H), 8.32 (s, 1H), 8.07 (ddd, J = 8.3, 2.7, 1.4 Hz, 1H), 7.47 (dd, J =8.3, 4.7 Hz, 1H), 7.37 (ddd, J = 8.9, 6.6, 2.1 Hz, 1H), 7.29 (ddd, J =6.7, 1.9, 0.6 Hz, 1H), 6.53 (dt, J = 9.2, 1.0 Hz, 1H), 6.22 (td, J =6.7, 1.3 Hz, 1H), 4.65 (brs, 2H), 3.75 (q, IR (thin film) 1657 cm⁻¹ J =7.1 Hz, 2H), 1.19 (t, J = 7.2 Hz, 3H) F123

White Semi- Solid ESIMS 376.1 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.99 (d, J =2.5 Hz, 1H), 8.62 (dd, J = 4.7, 1.3 Hz, 1H), 8.13 (s, 1H), 8.02 (ddd, J= 8.4, 2.7, 1.4 Hz, 1H), 7.45 (ddd, J = 8.3, 4.8, 0.5 Hz, 1H), 4.19-3.77 (m, 2H), 3.70 (dd, J = 14.1, 7.0 Hz, 2H), 3.45 (s, 2H), 2.61-2.49(m, 2H), 1.74 (s, 6H), 1.16 (t, J = 7.2 Hz, 3H) IR (thin film) 1677,1629 cm⁻¹ F124

Light Yellow Oil ESIMS 348.9 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.98 (d, J =2.6 Hz, 1H), 8.63 (dd, J = 4.8, 1.4 Hz, 1H), 8.09 (s, 1H), 8.03 (ddd, J= 8.3, 2.7, 1.5 Hz, 1H), 7.46 (dd, J = 8.3, 4.8 Hz, 1H), 3.90 (s, 2H),3.70 (q, J = 7.1 Hz, 2H), 3.54 (t, J = 6.9 Hz, 2H), 2.39 (t, J = 8.2 Hz,2H), 2.14-2.04 (m, 2H), 1.16 (t, J = 7.2 Hz, 3H) IR (thin film) 1664cm⁻¹ F125

Light Brown Gum ESIMS 440.3 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.98 (td, J =6.3, 2.7 Hz, 1H), 8.63 (dd, J = 7.6, 4.8 Hz, 1H), 8.12-8.02 (m, 1H),7.95 (s, 1H), 7.47 (td, J = 8.3, 4.5 Hz, 1H), 6.00-5.83 (m, 1H),3.88-3.58 (m, 5H), 3.54 (d, J = 4.6 Hz, 1H), 2.40 (t, J = 7.1 Hz, 1H),2.33 (d, J = 6.7 Hz, 1H), 2.27 (dd, IR (thin film) 3081, 2976, 1718,1649 cm⁻¹ J = 6.9, 3.3 Hz, 2H), 1.35- 0.95 (m, 3H), 1.15-0.95 (m, 1H),0.63-0.47 (m, 2H), 0.16 (dq, J = 24.0, 5.1 Hz, 2H) F126

White Foam ESIMS 412 ([M − H]⁻) (400 MHz, CDCl₃) δ 9.01 (d, J = 2.6 Hz,1H), 8.63 (dd, J = 4.7, 1.4 Hz, 1H), 8.46 (d, J = 8.9 Hz, 1H), 8.29 (s,1H), 8.10 (ddd, J = 8.3, 2.7, 1.5 Hz, 1H), 7.49 (dd, J = 8.4, 4.7 Hz,1H), 5.94 (dt, J = 5.6, 2.1 Hz, 1H), 5.88 (dd, J = 5.6, 2.6 Hz, 1H),5.07-4.99 (m, 1H), 3.68 (dq, J = 8.0, 1.9 Hz, 1H), ¹⁹F NMR (376 MHz,CDCl₃) δ −76.11 3.28 (s, 3H), 2.28 (dt, J = 13.8, 8.0 Hz, 1H), 2.03-1.98(m, 1H) F127

Light Yellow Gum ESIMS 520 ([M + H]⁺) (400 MHz, CDCl₃) δ 9.01 (d, J =2.4 Hz, 1H), 8.64 (d, J = 3.6 Hz, 1H), 8.09 (dd, J = 8.0 Hz, 1.2 Hz,1H), 8.02 (s, 1H), 7.62 (d, J = 8.0 Hz, 2H), 7.48 (dd, J = 8.4 Hz, 4.8Hz, 1H), 7.35 (d, J = 8.4 Hz, 2H), 4.41 (s, 2H), 3.71 (q, J = 7.2 Hz,2H), 3.28 (t, IR (KBr): 3091, 2927, 2308, 1743, 1666, 1440, 1325 cm⁻¹ J= 5.2 Hz, 1H), 3.19-3.18 (m, 1H), 2.90 (dd, J = 5.2 Hz, 2.0 Hz, 1H),2.22 (t, J = 6.8 Hz, 2H), 1.77-1.73 (m, 4H), 1.17 (t, J = 7.2 Hz, 3H)F128

White Foam HRMS-ESI [M + Na]⁺ calcd for C₂₂H₂₈ClN₅NaO₄, 484.1722; found,484.1744 (400 MHz, CDCl₃) δ 8.98 (dd, J = 2.7, 0.8 Hz, 1H), 8.62 (dd, J= 4.8, 1.4 Hz, 1H), 8.06 (ddd, J = 8.4, 2.7, 1.5 Hz, 1H), 8.02 (s, 1H),7.45 (ddd, J = 8.3, 4.8, 0.8 Hz, 1H), 3.83-3.60 (m, 3H), 3.54 (ddd, J =10.9, 9.0, 7.3 Hz, 1H), 2.54 (p, J = 7.7 Hz, IR (thin film) 3512, 3096,1776, 1714, 1665 cm⁻¹ 1H), 2.38 (tq, J = 16.0, 7.7, 6.7 Hz, 2H), 2.17(dddd, J = 11.9, 8.4, 7.3, 3.2 Hz, 1H), 1.99 (dq, J = 14.2, 7.3 Hz, 1H),1.86 (tt, J = 14.2, 7.0 Hz, 1H), 1.67 (s, 1H), 1.50 (s, 9H), 1.15 (t, J= 7.2 Hz, 3H) F129

Light Brown Gum ESIMS 506 ([M + H]⁺) (300 MHz, CDCl₃) δ 8.98 (d, J = 2.4Hz, 1H), 8.62 (d, J = 3.9 Hz, 1H), 8.07-8.00 (M, 2H), 7.60 (d, J = 7.8Hz, 2H), 7.45 (dd, J = 8.4 Hz, 4.8 Hz, 1H), 7.32 (d, J = 7.8 Hz, 2H),4.45-4.30 (m, 2H), 3.78-3.62 (m, 2H), 3.30- 3.21 (m, 2H), 2.86 (dd, J =1.8 Hz, 5.4 Hz, 1H), 2.40- IR (KBr): 1737, 1658, 1643, 1585, 1487, 1327,1142 cm⁻¹ 2.35 (m, 2H), 2.14-1.91 (m, 2H), 1.15 (t, J = 7.2 Hz, 3H) F130

Yellow Oil ESIMS 364 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.93 (d, J = 2.4 Hz,1H), 8.62 (m, 1H), 8.04 (ddd, J = 8.3, 2.7, 1.4 Hz, 1H), 7.98 (s, 1H),7.46 (dd, J = 8.3, 4.7 Hz, 1H), 4.21 (dt, J = 12.4, 6.2 Hz, 1H), 3.24(s, 3H), 2.52 (t, J = 6.8 Hz, 2H), 2.42 (t, J = 6.8 Hz, 2H), 1.79 (s,3H), 1.17 (d, J = 6.2 Hz, 6H). Mixture of E and Z isomer in 9:1 ratiomajor isomer reported F131

Yellow Viscous Oil HRMS-ESI [M + H]⁺ calcd for C₁₇H₂₁ClN₅O₂, 362.1378;found, 362.1408 (400 MHz, CDCl₃) δ 9.05- 8.95 (m, 1H), 8.61 (dd, J =4.8, 1.4 Hz, 1H), 8.09-7.98 (multiple peaks, 2H), 7.44 (ddd, J = 8.3,4.8, 0.8 Hz, 1H), 5.41 (s, 1H), 3.70 (ddt, J = 18.7, 13.6, 6.8 Hz, 2H),3.36-3.19 (m, 2H), 2.49- 2.21 (m, 4H), 1.99 (dq, J = 14.1, 6.9 Hz, 1H),1.90- 1.71 (m, 2H), 1.15 (t, J = 7.2 IR (thin film) 3284, 1659 cm⁻¹ Hz,3H) P1

Colorless Oil ESIMS 444 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.98 (dd, J = 2.7,0.8 Hz, 1H), 8.62 (dd, J = 4.8, 1.5 Hz, 1H), 8.05 (ddd, J = 8.4, 2.7,1.5 Hz, 1H), 8.02 (s, 1H), 7.45 (ddd, J = 8.4, 4.8, 0.8 Hz, 1H), 3.82(q, J = 9.1 Hz, 2H), 3.70 (dq, J = 9.8, 6.8 Hz, 2H), 3.47-3.34 (m, 2H),2.54-2.40 (m, 1H), 2.40- ¹³C NMR (101 MHz, CDCl₃) δ 177.22, 172.5,148.5, 140.8, 140.2, 135.7, 126.6, 126.4, 124.0, 124.0, 46.2, 44.3,44.0, 43.8, 39.8, 2.32 (m, 2H), 2.32-2.21 (m, 31.0, 26.6, 1H), 1.98 (dq,J = 14.3, 7.1 25.4, 13.1 Hz, 1H), 1.86 (dq, J = 14.4, 7.4 Hz, 1H), 1.73(dq, J = 12.8, 8.4 Hz, 1H), 1.15 (t, J = 7.1 Hz, 3H) P16

White semi- solid ESIMS 444 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.97 (d, J =2.7 Hz, 1H), 8.64 (dd, J = 4.7, 1.5 Hz, 1H), 8.07 (ddd, J = 8.3, 2.7,1.4 Hz, 1H), 7.98 (s, 1H), 7.48 (ddd, J = 8.3, 4.8, 0.8 Hz, 1H), 4.53(d, J = 13.2 Hz, 1H), 3.79 (d, J = 14.0 Hz, 1H), IR (thin film) 1648cm⁻¹ 3.70 (s, 2H), 3.22 (qd, J = 10.1, 2.1 Hz, 2H), 3.03 (t, J = 12.8Hz, 1H), 2.67-2.42 (m, 2H), 1.90-1.66 (m, 3H), 1.15 (t, J = 7.1 Hz, 3H)One aliphatic proton not located. P20

White solid 43-46° C. ESIMS 362 ([M + H]⁺) (600 MHz, CDCl₃) δ 9.02- 8.93(m, 1H), 8.64 (ddd, J = 6.1, 4.7, 1.4 Hz, 1H), 8.09- 8.02 (m, 1H), 8.01(d, J = 2.5 Hz, 1H), 7.47 (dddd, J = 10.1, 8.3, 4.7, 0.8 Hz, 1H), 3.72(ddd, J = 15.2, 10.1, 4.8 Hz, 2H), 3.69-3.58 (m, 3H), 3.56-3.46 (m, 2H),3.38 (dt, J = 9.9, 7.7 Hz, 1H), IR (thin film) 1626 cm⁻¹ 2.96 (p, J =7.6 Hz, 1H), 2.01 (s, 3H), 1.16 (t, J = 7.2 Hz, 3H) Compound exists as60:40 mixture of rotamers, only signals of major rotamer reported. P21

White semi- solid ESIMS 430 ([M + H]⁺) (400 MHz, CDCl₃) δ 9.01- 8.94 (m,1H), 8.65 (ddd, J = 4.6, 2.9, 1.4 Hz, 1H), 8.12- 7.98 (m, 2H), 7.53-7.43(m, 1H), 3.87-3.53 (m, 5H), 3.44 (dt, J = 9.6, 7.6 Hz, 1H), 3.13 (qd, J= 10.2, 7.0 Hz, 2H), 3.00 (p, J = 7.4 Hz, 1H), 2.45-2.32 (m, 1H), IR(thin film) 1653 cm⁻¹ 2.16-2.03 (m, 1H), 1.35- 1.07 (m, 3H) Compoundexists as a mixture of 6:4 mixture of rotamers, only the signals ofmajor rotamer is reported. P23

White solid 42-45° C. ESIMS 348 ([M + H]⁺) (600 MHz, CDCl₃) δ 8.98- 8.90(m, 1H), 8.65 (dd, J = 4.8, 1.4 Hz, 1H), 8.03 (ddd, J = 8.4, 2.6, 1.4Hz, 1H), 7.91 (s, 1H), 7.47 (ddd, J = 8.3, 4.8, 0.8 Hz, 1H), 4.47 (t, J= 7.1 Hz, 1H), 4.05 (t, J = 8.2 Hz, 2H), 3.86 (t, J = 9.3 Hz, 1H), 3.74(s, 2H), 3.38 (tt, J = 8.9, 6.2 Hz, 1H), IR (thin film) 1644 cm⁻¹ 1.84(s, 3H), 1.18 (t, J = 7.2 Hz, 3H) P24

Colorless oil ESIMS 416 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.99- 8.91 (m,1H), 8.65 (dd, J = 4.8, 1.4 Hz, 1H), 8.03 (ddd, J = 8.3, 2.7, 1.4 Hz,1H), 7.94 (s, 1H), 7.48 (ddd, J = 8.4, 4.8, 0.8 Hz, 1H), 4.55 (dd, J =8.2, 6.1 Hz, 1H), 4.13 (q, J = 6.8, 5.0 Hz, 2H), 3.93 (t, J = 9.6 Hz,1H), IR (thin film) 1664 cm⁻¹ 3.84-3.67 (m, 2H), 3.43 (tt, J = 8.9, 6.2Hz, 1H), 2.94 (qd, J = 10.4, 1.6 Hz, 2H), 1.18 (t, J = 7.2 Hz, 3H) FA1

Light yellow oil ESIMS 416 ([M + H]⁺) (400 MHz, DMSO-d₆) δ 9.05 (dd, J =2.7, 0.8 Hz, 1H), 8.82 (s, 1H), 8.59 (dd, J = 4.8, 1.4 Hz, 1H), 8.20(ddd, J = 8.4, 2.8, 1.4 Hz, 1H), 7.67 (d, J = 2.4 Hz, 1H), 7.59 (ddd, J= 8.4, 4.8, 0.8 Hz, 1H), 6.39 (d, J = 2.3 Hz, 1H), 4.32 (t, J = 6.8 Hz,2H), 3.84 (s, 3H), 3.57 (m, 2H), 2.66 (t, J = 6.5 Hz, 2H), 2.05 (s, 3H),1.05 (t, J = 7.1 Hz, 3H) IR (thin film) 3014, 2973, 2932, 1661, 1440cm⁻¹ FA2

Colorless gum ESIMS 444 ([M + H]⁺) (400 MHz, DMSO-d₆) δ δ 9.05 (dd, J =2.7, 0.8 Hz, 1H), 8.83 (d, J = 1.1 Hz, 1H), 8.59 (dd, J = 4.7, 1.4 Hz,1H), 8.20 (ddd, J = 8.4, 2.8, 1.4 Hz, 1H), 7.66 (d, J = 2.3 Hz, 1H),7.59 (ddd, J = 8.3, 4.7, 0.8 Hz, 1H), 6.39 (d, J = 2.3 Hz, 1H), 4.31 (m,3H), 3.57 (d, J = 7.3 Hz, 2H), 2.66 (t, J = 6.7 Hz, 2H), 2.04 (s, 3H),1.21 (d, J = 6.2 Hz, 6H), 1.05 (t, J = 7.1 Hz, 3H) IR (thin film) 3010,741,440 cm⁻¹ FA3

White semi- solid ESIMS 404 ([M + H]⁺) (400 MHz, CDCl₃) δ 9.13 (d, J =2.6 Hz, 1H), 8.62 (dd, J = 4.8, 1.5 Hz, 1H), 8.28- 8.18 (m, 2H),7.49-7.39 (m, 1H), 4.70-4.61 (m, 1H), 4.06 (dd, J = 13.8, 7.1 Hz, 1H),3.83 (d, J = 13.5 Hz, 1H), 3.70 (d, J = 37.1 Hz, 1H), 3.37 (dq, J =14.2, 7.2 Hz, 1H), 3.12-2.97 (m, 1H), 2.77-2.62 (m, 2H), 2.40- 2.32 (m,1H), 1.87 (d, J = IR (thin film) 1647 cm⁻¹ 4.1 Hz, 1H), 1.42-1.22 (m,2H), 1.13 (t, J = 7.2 Hz, 3H), 1.09 (d, J = 6.7 Hz, 3H), 0.99 (d, J =6.7 Hz, 3H) Two rotational isomers, only signals of major isomerreported. FA4

Colorless gum ESIMS 460 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.95 (s, 1H), 8.63(d, J = 4.6 Hz, 1H), 8.05 (ddd, J = 8.3, 2.7, 1.4 Hz, 1H), 7.94 (s,0.8H), 7.93 (s, 0.2H), 7.46 (dd, J = 8.3, 4.7 Hz, 1H), 3.98 (t, J = 5.9Hz, 1.6H), 3.91 (t, J = 6.2 Hz, 0.4H), 3.71 (q, J = 7.2 Hz, 2H), 2.58(dd, J = 8.4, 7.0 Hz, 0.4H), 2.51 IR (thin film) 3092, 2935, 2874, 1663cm⁻¹ (dd, J = 8.3, 6.3 Hz, 1.6H), 2.41-2.30 (m, 2H), 2.16-1.99 (m, 2H),1.85 (s, 0.6H), 1.80 (s, 2.4H), 1.72-1.62 (m, 4H), 1.16 (td, J = 7.2,1.9 Hz, 3H) FA5

White solid 62-66° C. ESIMS 430 ([M + H]⁺) (600 MHz, CDCl₃) δ 8.97 (d, J= 2.7 Hz, 1H), 8.65 (dd, J = 4.8, 1.4 Hz, 1H), 8.07 (ddd, J = 8.4, 2.7,1.4 Hz, 1H), 7.98 (s, 1H), 7.48 (ddd, J = 8.4, 4.7, 0.8 Hz, 1H), 4.42(d, J = 13.3 Hz, 1H), 4.00 (d, J = 14.0 Hz, 1H), 3.75-3.59 (m, 2H), 3.08(t, IR (thin film) 1684 cm⁻¹ J = 12.9 Hz, 1H), 2.79 (t, J = 12.8 Hz,1H), 2.56 (td, J = 10.4, 5.1 Hz, 1H), 1.95- 1.68 (m, 4H), 1.16 (t, J =7.1 Hz, 3H) FA6

Yellow solid 142-143° C. ESIMS 458 ([M + H]⁺) (600 MHz, CDCl₃) δ 8.97(d, J = 2.7 Hz, 1H), 8.64 (dd, J = 4.7, 1.4 Hz, 1H), 8.07 (ddd, J = 8.3,2.6, 1.4 Hz, 1H), 7.98 (s, 1H), 7.48 (dd, J = 8.3, 4.7 Hz, 1H), 4.52 (d,J = 13.3 Hz, 1H), 3.82 (d, J = 13.7 Hz, 1H), 3.77-3.59 IR (thin film)1646 cm⁻¹ (m, 2H), 2.95 (t, J = 12.8 Hz, 1H), 2.51 (ddq, J = 18.7, 13.6,9.8, 9.1 Hz, 6H), 1.87- 1.66 (m, 4H), 1.15 (t, J = 7.2 Hz, 3H) FA7

Yellow solid 160-161° C. ESIMS 415 ([M + H]⁺) (600 MHz, CDCl₃) δ 8.98(d, J = 2.7 Hz, 1H), 8.64 (dd, J = 4.8, 1.4 Hz, 1H), 8.07 (ddd, J = 8.4,2.7, 1.4 Hz, 1H), 7.99 (s, 1H), 7.52-7.43 (m, 1H), 4.50 (d, J = 13.4 Hz,1H), 3.78 (d, J = 13.8 Hz, 1H), 3.74-3.63 (m, 2H), IR (thin film) 1642cm⁻¹ 2.96 (t, J = 12.8 Hz, 1H), 2.75-2.60 (m, 4H), 2.60-2.43 (m, 2H),1.89-1.66 (m, 4H), 1.15 (t, J = 7.1 Hz, 3H) FA8

White semi- solid ESIMS 439 ([M + H]⁺) (600 MHz, CDCl₃) δ 8.97 (d, J =2.8 Hz, 1H), 8.65 (ddd, J = 8.6, 4.3, 2.0 Hz, 3H), 8.07 (ddd, J = 8.4,2.7, 1.4 Hz, 1H), 7.98 (s, 1H), 7.73 (dt, J = 7.9, 1.9 Hz, 1H), 7.48(dd, J = 8.4, 4.7 Hz, 1H), 7.35 (ddd, J = 8.0, 4.8, 1.0 Hz, 1H),4.66-4.52 IR (thin film) 1624 cm⁻¹ (m, 1H), 3.88-3.56 (m, 3H), 3.07-2.88(m, 1H), 2.82- 2.66 (m, 1H), 2.54 (td, J = 10.8, 5.2 Hz, 1H), 1.97-1.63(m, 4H), 1.16 (t, J = 7.2 Hz, 3H) FA9

Colorless oil ESIMS 416 ([M + H]⁺) (600 MHz, CDCl₃) δ 8.97 (dd, J = 7.2,2.7 Hz, 1H), 8.65 (dt, J = 4.8, 1.6 Hz, 1H), 8.10-8.03 (m, 1H), 8.00 (d,J = 0.8 Hz, 1H), 7.48 (dddd, J = 9.0, 4.6, 3.3, 0.8 Hz, 1H), 4.04-3.62(m, 5H), 3.62-3.53 (m, 1H), 3.03 (p, J = 7.7 Hz, 1H), IR (thin film)1683 cm⁻¹ 2.43-2.29 (m, 1H), 2.14- 2.07 (m, 1H), 1.19-1.16 (m, 3H)Compound exists as a ~6:4 mixture of rotamers, only signals of majorrotamer was reported. FA10

White semi- solid ESIMS 444 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.97 (t, J =3.1 Hz, 1H), 8.64 (ddd, J = 4.7, 3.1, 1.4 Hz, 1H), 8.09-8.01 (m, 1H),8.00 (d, J = 2.2 Hz, 1H), 7.47 (dtd, J = 8.3, 5.0, 0.8 Hz, 1H),3.86-3.48 (m, 5H), 3.39 (dt, J = 9.8, 7.6 Hz, IR (thin film) 1646 cm⁻¹1H), 2.98 (p, J = 7.4 Hz, 1H), 2.62-2.38 (m, 4H), 2.14-2.02 (m, 1H),1.99 (s, 1H), 1.29-1.10 (m, 3H) FA11

Yellow semi- solid ESIMS 401 ([M + H]⁺) (600 MHz, CDCl₃) δ 9.00- 8.93(m, 1H), 8.64 (td, J = 4.7, 1.4 Hz, 1H), 8.09-8.02 (m, 1H), 8.00 (d, J =4.5 Hz, 1H), 7.47 (dddd, J = 8.4, 7.6, 4.8, 0.8 Hz, 1H), 3.83-3.47 (m,4H), 3.38 (dt, J = 9.8, 7.6 Hz, 1H), 2.99 (p, J = IR (thin film) 1645cm⁻¹ 7.4 Hz, 1H), 2.64 (dddt, J = 45.4, 15.8, 13.2, 7.7 Hz, 4H),2.42-2.33 (m, 1H), 2.12-2.03 (m, 1H), 2.03- 1.94 (m, 1H), 1.24-1.12 (m,3H) FA12

Colorless oil ESIMS 425 ([M + H]⁺) (600 MHz, CDCl₃) δ 8.96 (d, J = 45.6Hz, 1H), 8.81- 8.72 (m, 1H), 8.65 (ddt, J = 7.9, 6.1, 3.0 Hz, 2H), 8.10-7.99 (m, 2H), 7.88-7.79 (m, 1H), 7.47 (dt, J = 8.3, 5.4 Hz, 1H),7.40-7.31 (m, 1H), 3.88-3.53 (m, 5H), 3.44 (dt, J = 10.3, 7.5 Hz, 1H),3.09 IR (thin film) 1621 cm⁻¹ (p, J = 7.6 Hz, 1H), 2.04- 1.96 (m, 1H),1.19 (t, J = 7.2 Hz, 3H) Compounds exists as a mixture of two rotamers,only the signals of major rotamer was reported, one aliphatic proton notlocated. FA13

White semi- solid ESIMS 434 ([M + H]⁺) (400 MHz, CDCl₃) δ 9.05- 8.89 (m,1H), 8.59 (dd, J = 4.8, 1.5 Hz, 1H), 8.13 (s, 1H), 8.02 (ddd, J = 8.4,2.6, 1.4 Hz, 1H), 7.43 (dd, J = 8.4, 4.8 Hz, 1H), 4.92-4.74 (m, 1H),3.93-3.74 (m, 2H), 3.73-3.06 (m, 2H), 1.89 (d, J = 13.4 Hz, 1H),1.80-1.52 (m, 5H), 1.50-1.26 (m, 9H), 1.15 (t, J = 7.1 Hz, 3H) IR (thinfilm) 1670 cm⁻¹ FA14

Colorless oil ESIMS 402 ([M + H]⁺) (400 MHz, CDCl₃) δ 9.00- 8.91 (m,1H), 8.66 (dd, J = 4.8, 1.4 Hz, 1H), 8.04 (ddd, J = 8.3, 2.7, 1.5 Hz,1H), 7.94 (s, 1H), 7.49 (ddd, J = 8.3, 4.8, 0.8 Hz, 1H), 4.70 (t, J =8.0 Hz, 1H), 4.37- 4.22 (m, 2H), 4.04 (t, J = 9.8 Hz, 1H), 3.75 (d, J =IR (thin film) 1693 cm⁻¹ 7.7 Hz, 2H), 3.54 (tt, J = 9.0, 6.4 Hz, 1H),1.19 (t, J = 7.2 Hz, 3H) FA15

Colorless oil ESIMS 430 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.95 (d, J = 2.7Hz, 1H), 8.65 (dd, J = 4.8, 1.5 Hz, 1H), 8.04 (ddd, J = 8.4, 2.7, 1.4Hz, 1H), 7.93 (s, 1H), 7.48 (ddd, J = 8.3, 4.8, 0.7 Hz, 1H), 4.47 (dd, J= 8.2, 6.0 Hz, 1H), 4.16-4.01 (m, 2H), IR (thin film) 1655 cm⁻¹ 3.89 (t,J = 9.3 Hz, 1H), 3.74 (d, J = 7.8 Hz, 2H), 3.41 (tt, J = 8.9, 6.1 Hz,1H), 2.51- 2.38 (m, 2H), 2.36-2.23 (m, 2H), 1.18 (t, J = 7.2 Hz, 3H)FA16

White solid 49-52° C. ESIMS 387 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.99- 8.92(m, 1H), 8.65 (dd, J = 4.8, 1.4 Hz, 1H), 8.04 (ddd, J = 8.3, 2.7, 1.4Hz, 1H), 7.93 (s, 1H), 7.48 (ddd, J = 8.3, 4.8, 0.8 Hz, 1H), 4.52- 4.43(m, 1H), 4.09 (q, J = 9.3, 8.6 Hz, 2H), 3.91 (t, J = IR (thin film) 1655cm⁻¹ 9.4 Hz, 1H) 3.74 (d, J = 7.7 Hz, 2H), 3.44 (tt, J = 8.9, 6.2 Hz,1H), 2.75-2.56 (m, 2H), 2.48-2.38 (m, 2H), 1.18 (t, J = 7.2 Hz, 3H) FA17

Colorless oil ESIMS 387 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.95 (dd, J = 2.8,0.8 Hz, 1H), 8.85-8.79 (m, 1H), 8.69 (dd, J = 4.8, 1.7 Hz, 1H), 8.65 dd,J = 4.8, 1.4 Hz, 1H), 8.04 (ddd, J = 8.3, 2.7, 1.4 Hz, 1H), 7.98-7.93(m, 2H), 7.48 (ddd, J = 8.3, 4.8, 0.8 Hz, 1H), 7.37 (ddd, J = 7.9, 4.9,0.9 Hz, 1H), 4.67 (t, J = IR (thin film) 1655 cm⁻¹ 7.3 Hz, 1H), 4.25(dd, J = 20.9, 12.1 Hz, 2H), 4.12 (d, J = 9.5 Hz, 1H), 3.81-3.66 (m,2H), 3.51 (tt, J = 9.0, 6.3 Hz, 1H), 1.19 (t, J = 7.2 Hz, 3H) FA18

Yellow semi- solid ESIMS 434 ([M + H]⁺) (400 MHz, CDCl₃) δ 9.16- 8.97(m, 1H), 8.62 (dd, J = 4.8, 1.5 Hz, 1H), 8.20-8.07 (m, 2H), 7.49-7.38(m, 1H), 4.26-3.86 (m, 3H), 3.80- 3.17 (m, 3H), 3.03-2.54 (m, 2H), 2.35(ddd, J = 14.9, 10.4, 4.0 Hz, 1H), 1.91-1.69 (m, 2H), 1.36 (s, 9H), 1.13(t, J = 7.1 Hz, 3H) IR (thin film) 1667 cm⁻¹ FA19

Light yellow gum ESIMS 446 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.95 (d, J =2.7 Hz, 1H), 8.63 (dd, J = 4.8, 1.4 Hz, 1H), 8.04 (ddd, J = 8.3, 2.8,1.4 Hz, 1H), 7.93 (d, J = 2.1 Hz, 1H), 7.46 (ddd, J = 8.3, 4.8, 0.8 Hz,1H), 4.01 (t, J = 6.2 Hz, 2H), 3.71 (q, J = 7.2 Hz, 2H), 2.51 (dd, J =8.0, IR (thin film) 3092, 2935, 1663 cm⁻¹ 6.3 Hz, 2H), 2.36 (td, J =7.1, 6.6, 5.7 Hz, 2H), 2.24- 2.01 (m, 2H), 1.86 (q, J = 5.2, 4.6 Hz,2H), 1.81 (s, 3H), 1.20-1.10 (m, 3H) FA20

Light yellow gum ESIMS 410 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.95 (dd, J =2.7, 0.8 Hz, 1H), 8.62 (dd, J = 4.8, 1.5 Hz, 1H), 8.05 (ddt, J = 8.3,2.7, 1.3 Hz, 1H), 7.95 (s, 1H), 7.52-7.40 (m, 1H), 4.51 (t, J = 5.8 Hz,0.75H), 4.46 (t, J = 5.8 Hz, 0.25H), 4.39 (m, 0.75H), 4.34 (m, 0.25H),IR (thin film) 3092, 2964, 2932, 1663 cm⁻¹ 4.00 (t, J = 6.1 Hz, 1.5H),3.94 (s, 0.5H), 3.71 (q, J = 7.2 Hz, 2H), 2.57 (dd, J = 8.5, 7.0 Hz,0.5H), 2.55-2.46 (m, 1.5H), 2.37 (dd, J = 8.0, 6.5 Hz, 2H), 1.85 (s,0.9H), 1.80 (s, 2.1H), 1.77-1.62 (m, 4H), 1.16 (t, J = 7.2 Hz, 3H) FA21

Colorless gum ESIMS 440 ([M + H]⁺) (400 MHz, CDCl₃) δ 9.02- 8.87 (m,1H), 8.63 (m, 1H), 7.94 (s, 0.3H), 7.93 (s, 0.7H), 7.51-7.37 (m, 1H),4.00 (d, J = 6.0 Hz, 1.4H), 3.94 (d, J = 6.1 Hz, 2H), 2.70-2.55 (m, 2H),2.54- 2.44 (m, 2H), 2.35 (m, 6H), IR (thin film) 3092, 2933, 2870, 1664cm⁻¹ 1.85 (s, 1H), 1.80 (s, 2H), 1.21-1.08 (m, 3H) FA22

Light brown gum ESIMS 495 ([M + H]⁺) (400 MHz, CDCl₃) δ 9.04- 8.92 (m,1H), 8.73-8.52 (m, 2H), 8.06 (ddd, J = 8.3, 2.8, 1.4 Hz, 1H), 7.96 (s,1H), 7.80 (d, J = 8.1 Hz, 1H), 7.71-7.55 (m, 1H), 7.46 (ddd, J = 8.3,4.7, 0.8 Hz, IR (thin film) 3091, 2975, 2933, 1664, 1585, 1487, 1441,1459, 1401, 1428, 1377, 1333, 1H), 5.07 (s, 1.4H), 5.06 (s, 1305, 1266,0.6H), 3.65 (q, J = 7.2 Hz, 1174, 1130, 2H), 2.62 (m, 0.3H), 2.50 1084cm⁻¹ (t, J = 7.0 Hz, 1.7H), 2.36 (td, J = 7.5, 7.0, 4.9 Hz, 2H), 1.86(s, 2H), 1.85 (s, 1H), 1.18-1.14 (m, 1H), 1.12 (t, J = 7.2 Hz, 2H) FA23

Light brown gum ESIMS 474 ([M + H]⁺) (400 MHz, CDCl₃) δ 9.07 (d, J = 2.7Hz, 0.7H), 8.97 (d, J = 2.7 Hz, 0.3H), 8.61 (m, 1H), 8.35 (s, 0.7H),8.13 (ddd, J = 8.4, 2.7, 1.5 Hz, 0.7H), 8.07 (s, 0.3H), 8.05 (dd, J =2.7, 1.5 Hz, 0.3H), 7.46 (ddd, J = 8.3, 4.7, 0.8 Hz, 1H), 5.30 (s,0.6H), IR (thin film) 3095, 2974, 2934, 1668 cm⁻¹ 5.04 (s, 1.4H), 3.67(q, J = 7.9, 7.1 Hz, 2H), 2.61 (t, J = 7.6 Hz, 0.6H), 2.51 (d, J = 6.6Hz, 1.4H), 2.45 (d, J = 7.6 Hz, 0.6H), 2.36 (d, J = 6.8 Hz, 1.4H), 1.88(d, J = 1.9 Hz, 0.9H), 1.85 (s, 2.1H), 1.41 (s, 6.3H), 1.39 (s, 2.7H),1.14 (t, J = 7.2 Hz, 3H) FA24

Light brown gum ESIMS 529 ([M + H]⁺) (400 MHz, CDCl₃) δ 9.01 (dd, J =2.7, 0.7 Hz, 0.7H), 8.94-8.89 (m, 0.3H), 8.68 (dd, J = 2.0, 1.0 Hz,0.7H), 8.63 (dd, J = 4.7, 1.5 Hz, 1.3H), 8.13 (s, 0.7H), 8.11- 8.06 (m,1H), 8.02 (ddd, J = 8.4, 2.8, 1.5 Hz, 0.3H), 7.92- 7.84 (m, 0.7H), 7.81(d, J = IR (thin film) 3090, 2974, 2934, 1664 cm⁻¹ 2.0 Hz, 0.3H),7.50-7.41 (m, 1H), 5.27 (s, 1.4H), 5.20 (s, 0.6H), 3.65 (q, J = 7.4 Hz,2H), 2.63 (dd, J = 8.4, 6.9 Hz, 0.6H), 2.49 (t, J = 7.1 Hz, 1.4H),2.46-2.38 (m, 0.6H), 2.33 (t, J = 7.1 Hz, 1.4H), 1.85 (s, 2.1H), 1.84(s, 0.9H), 1.16 (t, J = 7.1 Hz, 0.9H), 1.12 (t, J = 7.2 Hz, 2.1H) FA25

Light brown gum ESIMS 445 ([M +H]⁺) (400 MHz, CDCl₃) δ 8.97 (td, J =3.0, 1.5 Hz, 1H), 8.63 (dd, J = 4.7, 1.4 Hz, 1H), 8.07 (ddd, J = 8.3,2.9, 1.4 Hz, 1H), 7.94 (s, 0.8H), 7.90 (s, 0.2H), 7.48 (ddd, J = 8.4,4.8, 0.7 Hz, 1H), 4.70 (d, J = 7.4 Hz, 1.6H), 4.65 (s, 0.4H), 3.70 (q, J= 7.0 Hz, 2H), 2.57-2.46 (m, IR (thin film) 3092, 2972, 2931, 1664 cm⁻¹2H), 2.42-2.34 (m, 2H), 2.33 (s, 0.6H), 2.30 (s, 2.4H), 2.20 (s, 2.4H),1.83 (s, 0.6H), 1.76 (s, 3H), 1.20- 1.10 (m, 3H) FA26

Light yellow gum ESIMS 514 ([M + H]⁺) (400 MHz, CDCl₃) δ 9.05- 8.86 (m,1H), 8.62 (dd, J = 4.8, 1.5 Hz, 1H), 8.02 (ddd, J = 8.3, 2.7, 1.5 Hz,1H), 7.80 (s, 1H), 7.45 (ddd, J = 8.3, 4.8, 0.8 Hz, 1H), 7.25 (m, 2H),6.99 (dd, J = 5.1, 3.8 Hz, 1H), 4.04 (t, J = 6.0 Hz, 2H), 3.67 (m, 2H),3.03 (dd, J = 8.4, 7.1 Hz, 2H), 2.42 (dd, J = 8.4, 7.2 Hz, IR (thinfilm) 3090, 2972, 2973, 1662 cm⁻¹ 2H), 2.17-2.02 (m, 2H), 1.92-1.84 (m,2H), 1.09 (t, J = 7.2 Hz, 3H) FA27

Light yellow gum ESIMS 514 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.90 (d, J =2.6 Hz, 1H), 8.48 (d, J = 4.8 Hz, 1H), 8.01 (ddd, J = 8.3, 2.7, 1.4 Hz,1H), 7.82 (s, 1H), 7.51-7.41 (m, 3H), 7.06 (dd, J = 5.2, 3.9 Hz, 1H),4.22 (t, J = 6.1 Hz, 2H), 3.71 (q, J = 7.2 Hz, 2H), 3.12 (t, J = 7.1 Hz,2H), IR (thin film) 3092, 2972, 2934, 1662 cm⁻¹ 2.58-2.50 (m, 2H),2.32-2.15 (m, 2H), 2.03-1.90 (m, 2H), 1.15 (t, J = 7.2 Hz, 3H) FA28

Light brown gum ESIMS 528 ([M + H]⁺) (400 MHz, CDCl₃) δ 9.02- 8.84 (m,1H), 8.62 (dd, J = 4.7, 1.4 Hz, 1H), 8.02 (ddd, J = 8.4, 2.7, 1.4 Hz,1H), 7.79 (s, 1H), 7.45 (ddd, J = 8.4, 4.8, 0.8 Hz, 1H), 7.24- 7.19 (m,2H), 6.99 (dd, J = 5.1, 3.7 Hz, 1H), 3.98 (t, J = 6.2 Hz, 2H), 3.66 (d,J = 7.8 Hz, 2H), 3.02 (dd, J = 8.2, IR (thin film) 3089, 2936, 2875,1662 cm⁻¹ 7.2 Hz, 2H), 2.42 (t, J = 7.7 Hz, 2H), 2.09-1.95 (m, 2H), 1.64(dt, J = 13.4, 6.5 Hz, 2H), 1.52 (m, 2H), 1.07 (t, J = 7.2 Hz, 3H) FA29

Light brown gum ESIMS 528 ([M + H]⁺) (400 MHz, CDCl₃) δ 9.02- 8.84 (m,1H), 8.62 (dd, J = 4.7, 1.4 Hz, 1H), 8.02 (ddd, J = 8.4, 2.7, 1.4 Hz,1H), 7.79 (s, 1H), 7.45 (ddd, J = 8.4, 4.8, 0.8 Hz, 1H), 7.24- 7.19 (m,2H), 6.99 (dd, J = 5.1, 3.7 Hz, 1H), 3.98 (t, J = 6.2 Hz, 2H), 3.66 (d,J = 7.8 Hz, 2H), 3.02 (dd, IR (thin film) 3095, 2970, 2933, 1661 cm⁻¹ J= 8.2, 7.2 Hz, 2H), 2.42 (t, J = 7.7 Hz, 2H), 2.09- 1.95 (m, 2H), 1.64(dt, J = 13.4, 6.5 Hz, 2H), 1.52 (m, 2H), 1.07 (t, J = 7.2 Hz, 3H) FA30

Light brown gum ESIMS 508 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.93 (d, J = 2.6Hz, 1H), 8.62 (dd, J = 4.8, 1.4 Hz, 1H), 8.03 (ddd, J = 8.3, 2.7, 1.4Hz, 1H), 7.81 (s, 1H), 7.45 (ddd, J = 8.3, 4.8, 0.8 Hz, 1H), 7.24 (m,2H), 6.99 (dd, J = 5.1, 3.7 Hz, 1H), 4.02 (d, J = 6.3 Hz, 2H), 3.67 (m,2H), 3.02 (dd, J = 8.4, 7.1 Hz, 2H), 2.64-2.48 (m, 2H), 2.42 (dd, J =8.4, 7.2 Hz, IR (thin film) 3089, 2932, 1664 cm⁻¹ 2H), 2.36-2.18(m, 3H),1.09 (t, J = 7.1 Hz, 3H) FA31

Light brown gum ESIMS 508 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.92- 8.89 (m,1H), 8.62 (dd, J = 4.7, 1.4 Hz, 1H), 8.01 (ddd, J = 8.3, 2.7, 1.5 Hz,1H), 7.83 (s, 1H), 7.46 (tdd, J = 8.6, 4.9, 0.9 Hz, 3H), 7.05 (dd, J =5.1, 3.9 Hz, 1H), 4.21 (d, J = 6.2 Hz, 2H), IR (thin film) 3089, 2933,1664 cm⁻¹ 3.71 (q, J = 7.2 Hz, 2H), 3.07 (dd, J = 8.1, 6.6 Hz, 2H),2.74-2.57 (m, 2H), 2.54 (dd, J = 8.2, 6.6 Hz, 2H), 2.50-2.36 (m, 3H),1.31 (t, J = 7.1 Hz, 3H) FA32

Yellow oil ESIMS 376 ([M + H]⁺) 1H NMR (500 MHz, Chloroform-d) d 9.02(d, J = 2.8 Hz, 1H), 8.60 (dd, J = 4.9, 1.4 Hz, 1H), 8.01 (ddd, J = 8.4,2.7, 1.5 Hz, 1H), 7.42 (ddd, J = 8.3, 4.8, 0.8 Hz, 1H), 5.25-5.10 (m,1H), 4.08-3.68 (m, 3H), 3.67-3.56 (m, 1H), 2.02 (s, 3H), 1.98-1.68 (m,4H), 1.51-1.34 (m, 2H), 1.14 (t, J = 7.1 Hz, 3H) IR (thin film) 1633cm⁻¹ FA33

Yellow oil ESIMS 376 ([M + H]⁺) 1H NMR (500 MHz, Chloroform-d) d 9.02(dd, J = 2.8, 0.8 Hz, 1H), 8.61 (dd, J = 4.8, 1.4 Hz, 1H), 8.15 (s, 1H),8.07 (ddd, J = 8.4, 2.7, 1.5 Hz, 1H), 7.44 (ddd, J = 8.3, 4.8, 0.8 Hz,1H), 3.69 (q, J = 7.2 Hz, 2H), 3.39 (t, J = 7.1 Hz, 2H), 3.24 (t, J =6.7 Hz, 2H), 2.31 (t, J = 8.1 Hz, 2H), 2.18 (t, J = 6.7 Hz, IR (thinfilm) 1665 cm⁻¹ 2H), 2.05-1.93 (m, 2H), 1.87 (p, J = 6.7 Hz, 2H), 1.15(t, J = 7.2 Hz, 3H) FA34

Yellow oil ESIMS 378 ([M + H]⁺) 1H NMR (500 MHz, Chloroform-d) d 9.04(dd, J = 2.7, 0.8 Hz, 1H), 8.61 (dd, J = 4.8, 1.4 Hz, 1H), 8.18 (s, 1H),8.05 (ddd, J = 8.3, 2.7, 1.4 Hz, 1H), 7.44 (ddd, J = 8.3, 2.7, 1.4 Hz,1H), 7.44 (ddd, J = 8.4, 4.7, 0.8 Hz, 1H), 4.35-4.22 (m, 2H), 3.69 (q, J= 7.1 Hz, 2H), 3.59 (dd, J = 9.1, 7.0 Hz, 2H), 3.25 (t, J = 6.3 Hz, IR(thin film) 1739, 1660 cm⁻¹ 2H), 2.23 (t, J = 6.3 Hz, 2H), 1.92 (s, 2H),1.15 (t, J = 7.2 Hz, 3H) FA35

Light brown gum ESIMS 486 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.91 (dd, J =6.0, 2.6 Hz, 1H), 8.62 (dd, J = 4.8, 1.4 Hz, 0.75H), 8.47 (dd, J = 4.8,1.4 Hz, 0.25H), 8.01 (ddd, J = 8.3, 2.7, 1.4 Hz, 1H), 7.82 (d, J = 1.2Hz, 1H), 7.45 (ddd, J = 8.4, 4.8, 0.8 Hz, 1H), 7.39-7.32 (m, IR (thinfilm) 3091, 2974, 1660, 1154 cm⁻¹ 1H), 7.30 (dd, J = 5.1, 1.1 Hz, 1H),7.12-6.90 (m, 1H), 4.52 (q, J = 8.6 Hz, 0.5H), 4.39 (q, J = 8.5 Hz,1.5H), 3.78-3.60 (m, 2H), 3.14-3.02 (m, 2H), 2.54 (t, J = 7.3 Hz, 0.5H),2.49-2.40 (m, 1.5H), 1.20 (t, J = 6.6 Hz, 1H), 1.12 (t, J = 7.2 Hz, 2H)FA36

Light brown gum ESIMS 563 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.97- 8.89 (m,1H), 8.67-8.58 (m, 2H), 8.03 (ddd, J = 8.3, 2.7, 1.4 Hz, 1H), 7.83 (s,1H), 7.81-7.74 (m, 1H), 7.66- 7.59 (m 1H), 7.44 (ddd, J = 8.3, 4.8, 0.8Hz, 1H), 7.28 (d, J = 1.1 Hz, 1H), 7.25 (d, J = 1.1 Hz, 1H), 6.99 (dd, J= 5.1, 3.7 Hz, 1H), 5.12 (s, 2H), 3.77-3.51 (m, 2H), 3.08-3.00 (m, 2H),2.48- IR (thin film) 3086, 2972, 2932, 1662 cm⁻¹ 2.37 (m, 2H), 1.14-0.99(m, 3H) FA37

Light brown gum ESIMS 563 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.93 (d, J = 2.5Hz, 1H), 8.73 (d, J = 2.0 Hz, 1H), 8.62 (dd, J = 4.8, 1.5 Hz, 1H), 8.03(ddd, J = 8.3, 2.7, 1.4 Hz, 1H), 7.86 (s, 1H), 7.80 (m, 1H), 7.72-7.59(m, 2H), IR (thin film) 3086, 2972, 2932, 1662 cm⁻¹ 7.53-7.47 (m, 1H),7.45 (ddd, J = 8.3, 4.7, 0.8 Hz, 1H), 7.07 (dd, J = 4.9, 4.1 Hz, 1H),5.29 (d, J = 8.8 Hz, 2H), 3.67 (q, J = 7.1 Hz, 2H), 3.07 (t, J = 7.3 Hz,2H), 2.58-2.39 (m, 2H), 1.18- 1.01 (m, 3H) FA38

Light brown gum ESIMS 494 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.97- 8.87 (m,1H), 8.61 (dd, J = 4.7, 1.4 Hz, 1H), 8.02 (ddd, J = 8.3, 2.7, 1.4 Hz,1H), 7.83 (s, 1H), 7.44 (ddd, J = 8.3, 4.8, 0.8 Hz, 1H), 7.26 (m, 2H),7.00 (dd, J = 5.1, 3.7 Hz, 1H), 4.13-3.93 (m, 2H), 3.68 (m, 2H), 3.03(dd, J = 8.5, 7.1 Hz, 2H), 2.50- 2.38 (m, 2H), 1.97-1.86 (m, 1H), 1.41(tdd, J = 11.8, 7.8, 4.4 Hz, 1H), 1.14 (d, J = 4.7 Hz, 1H), 1.10 (t, J =7.2 Hz, 3H) IR (thin film) 3094, 2971, 2933, 1663 cm⁻¹ FA39

Light brown gum ESIMS 494 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.91 (d, J = 2.6Hz, 1H), 8.61 (dd, J = 4.7, 1.4 Hz, 1H), 8.02 (dd, J = 2.7, 1.5 Hz, 1H),7.83 (s, 1H), 7.49-7.42 (m, 3H), 7.04 (dd, J = 5.1, 3.9 Hz, 1H),4.25-4.16 (m, 2H), 3.71 (dd, J = 7.2, 3.6 Hz, 2H), 3.10-3.03 (m, 2H),2.56 (t, J = 7.3 Hz, 2H), 2.07- IR (thin film) 3095, 2970, 2931, 1662cm⁻¹ 1.92 (m, 1H), 1.48 (tdd, J = 11.9, 8.0, 4.5 Hz, 1H), 1.21 (dd, J =13.0, 3.9 Hz, 1H), 1.15 (t, J = 7.2 Hz, 3H) FA40

Light brown gum ESIMS 510 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.95- 8.89 (m,1H), 8.63 (dd, J = 4.7, 1.5 Hz, 1H), 8.01 (ddd, J = 8.3, 2.8, 1.4 Hz,1H), 7.60 (s, 1H), 7.45 (ddd, J = 8.4, 4.7, 0.8 Hz, 1H), 7.31 (d, J =8.6 Hz, 2H), 7.20- 7.10 (m, 2H), 4.97 (s, 2H), IR (thin film) 3092,2974, 2929, 1664 cm⁻¹ 3.67 (q, J = 7.1 Hz, 2H), 2.52 (dd, J = 7.9, 6.5Hz, 2H), 2.36 (dd, J = 7.8, 6.5 Hz, 2H), 1.86 (s, 3H), 1.13 (t, J = 7.2Hz, 3H) FA41

White semi- solid ESIMS 430 ([M + H]⁺) (500 MHz, CDCl₃) δ 9.03 (s, 1H),8.64 (td, J = 4.8, 1.4 Hz, 1H), 8.11-8.00 (m, 1H), 7.50-7.41 (m, 1H),4.55- 4.41 (m, 1H), 3.98-3.83 (m, 2H), 3.75-3.62 (m, 1H), 3.19-3.06 (m,1H), 2.95 (t, J = 12.1 Hz, 1H), 2.56-2.39 (m, 1H), 1.97-1.73 (m, 3H),1.47-1.34 (m, 1H), 1.16 (t, J = 7.2, 3H) IR (thin film) 1687, 1658 cm⁻¹Compound exists as two rotamers in 6:4 ratio. FA42

White semi- solid ESIMS 444 ([M + M]⁺) (500 MHz, CDCl₃) δ 9.07 (d, J =2.7 Hz, 1H), 8.64 (ddd, J = 11.6, 4.8, 1.4 Hz, 1H), 8.20-8.09 (m, 1H),7.51-7.40 (m, 1H), 4.69-4.58 (m, 1H), 4.07-3.95 (m, 1H), 3.79-3.59 (m,2H), 3.50- 3.33 (m, 1H), 3.24-3.06 (m, 3H), 2.76 (dd, J = 13.1, 11.0 Hz,1H), 2.46-2.31 (m, 1H), 1.97-1.79 (m, 2H), 1.42-1.26 IR (thin film) 1650cm⁻¹ (m, 1H), 1.14 (t, J = 7.2 Hz, 3H) Compound exists as two rotamersin 6:4 ratio. FA43

Yellow semi- solid ESIMS 458 ([M + H]⁺) (500 MHz, CDCl₃) δ 9.08 (s, 1H),8.64 (ddd, J = 7.4, 4.7, 1.4 Hz, 1H), 8.12 (ddd, J = 8.3, 2.6, 1.5 Hz,1H), 7.53-7.39 (m, 1H), 4.60 (d, J = 13.1 Hz, 1H), 4.02-3.92 (m, 1H),3.72 (d, J = 15.3 Hz, 2H), 3.43 (s, 1H), 3.06 (td, J = 13.2, 2.9 Hz,1H), IR (thin film) 1646 cm⁻¹ 2.73 (t, J = 12.0 Hz, 1H), 2.56-2.27 (m,5H), 1.88 (d, J = 9.0 Hz, 2H), 1.80 (dd, J = 13.7, 3.4 Hz, 1H), 1.14 (t,J = 7.2 Hz, 3H) Compound exists as two rotamers in 2:1 ratio, onlysignals of major rotamer reported. FA44

White semi- solid ESIMS 415 ([M + H]⁺) (500 MHz, CDCl₃) δ 9.08 (d, J =2.8 Hz, 1H), 8.64 (ddd, J = 7.5, 4.7, 1.4 Hz, 1H), 8.18-8.05 (m, 1H),7.52-7.41 (m, 1H), 4.59 (dd, J = 13.3, 3.7 Hz, 1H), 3.96 (s, 1H),3.71-3.58 (m, 1H), 3.50-3.39 (m, 1H), 3.07 (td, J = 13.3, 2.9 Hz, 1H),2.75 IR (thin film) 1643 cm⁻¹ (dd, J = 13.0, 11.0 Hz, 1H), 2.71-2.49 (m,5H), 2.42-2.31 (m, 1H), 1.97-1.77 (m, 2H), 1.34 (td, J = 12.6, 11.3, 6.1Hz, 1H), 1.14 (t, J = 7.1 Hz, 3H) Compound exists as a mixture of tworotamers in 7:3 ratio, only signals of major isomer reported. FA45

Yellow solid 52-54° C. ESIMS 376 ([M + H]⁺) (500 MHz, CDCl₃) δ 9.08 (d,J = 2.6 Hz, 1H), 8.63 (ddd, J = 15.1, 4.8, 1.4 Hz, 1H), 8.12 (ddd, J =8.3, 2.6, 1.4 Hz, 1H), 7.58-7.40 (m, 1H), 4.62 (d, J = 13.0 Hz, 1H),4.04-3.89 (m, 1H), 3.75-3.62 (m, 1H), 3.47-3.36 (m, 1H), 3.05 (td, J =13.2, 2.9 Hz, 1H), 2.67 (t, J = 12.0 Hz, 1H), 2.37 (ddd, J = IR (thinfilm) 1643 cm⁻¹ 15.1, 8.6, 3.9 Hz, 1H), 2.00 (s, 3H), 1.93-1.83 (m, 2H),1.76 (dt, J = 13.4, 3.4 Hz, 1H), 1.42-1.23 (m, 1H), 1.13 (t, J = 7.2 Hz,3H) Compound exists as a mixture of two rotamers in 7:3 ratio, onlysignals of major rotamer reported. FA46

Colorless oil ESIMS 336 ([M + H]⁺) (400 MHz, Benzene-d₆) δ 9.14 (s, 1H),8.85-8.54 (m, 1H), 8.24 (dd, J = 4.7, 1.5 Hz, 1H), 7.60 (ddd, J = 8.4,2.7, 1.4 Hz, 1H), 7.31 (s, 1H), 6.58 (ddd, J = 8.3, 4.8, 0.8 Hz, 1H),3.61 (q, J = 7.1 Hz, 2H), 2.51 (t, J = 7.1 Hz, 2H), 2.36 (t, J = 7.1 Hz,2H), 1.68 (s, 3H), 0.99 (t, J = 7.1 Hz, 3H) ¹³C NMR (101 MHz,Benzene-d₆) δ 171.7, 156.2, 148.0, 140.9, 139.6, 135.8, 126.5, 125.7,124.4, 123.8, 44.0, 31.3, 30.2, 14.1, 13.2 FA47

Colorless oil ESIMS 336 ([M + H]⁺) (400 MHz, Benzene-d₆) δ 9.17 (s, 1H),8.65 (d, J = 2.6 Hz, 1H), 8.19 (dd, J = 4.7, 1.5 Hz, 1H), 7.53 (ddd, J =8.3, 2.7, 1.5 Hz, 1H), 7.02 (t, J = 1.1 Hz, 1H), 6.53 (ddd, J = 8.3,4.7, 0.7 Hz, 1H), 3.58 (q, J = 7.1 Hz, 2H), 2.75 (t, J = 7.5 Hz, 2H),2.40 (t, J = 7.5 Hz, 2H), 1.73 ¹³C NMR (101 MHz, Benzene-d₆) δ 171.6,157.2, 147.9, 140.8, 139.6, 135.7, 126.4, 125.8, 124.3, 123.7, 43.9,30.0, 25.3, 20.3, (s, 3H), 0.98 (t, J = 7.1 Hz, 13.2 3H) FA48

Yellow oil ESIMS 321 ([M + H]⁺) (400 MHz, CDCl₃) δ 9.72 (s, 1H),9.04-8.97 (m, 1H), 8.68-8.58 (m, 1H), 8.06 (ddd, J = 8.4, 2.8, 1.5 Hz,1H), 7.51-7.38 (m, 2H), 3.93 (d, J = 24.4 Hz, 2H), 3.15 (dd, J = 18.9,10.1 Hz, 1H), 3.00-2.92 (m, 1H), 2.44 (dd, J = 18.8, 3.6 Hz, 1H), 1.15(t, J = 7.1 Hz, 3H), 1.10 (d, J = 6.9 Hz, 3H) FA49

Colorless oil (400 MHz, Benzene-d₆) δ 8.76-8.58 (m, 1H), 8.29 (dd, J =4.7, 1.5 Hz, 1H), 7.51 (ddd, J = 8.3, 2.8, 1.5 Hz, 1H), 6.97 (s, 1H),6.58 (ddd, J = 8.3, 4.8, 0.8 Hz, 1H), 3.92 (t, J = 6.3 Hz, 2H), 3.60 (q,J = 7.1 Hz, 2H), 2.55 (dd, J = 8.7, 6.8 Hz, 2H), 2.40- 2.33 (m, 3H),1.67 (s, 3H), ¹³C NMR (101 MHz, Benzene-d₆) δ 171.2, 155.8, 148.3,140.9, 139.7, 135.6, 126.0, 125.4, 124.5, 123.6, 71.9, 44.0, 31.3, 30.3,1.62 (dd, J = 14.3, 7.0 Hz, 27.0, 27.0, 1H), 1.49-1.38 (m, 1H), 20.0 (t,J = 1.25 (ddq, J = 14.7, 11.3, 10.9 Hz), 15.7 7.4 Hz, 1H), 1.00 (t, J =7.1 (t, J = 10.8 Hz, 3H), 0.91 (dddd, J = Hz), 14.7, 13.3 12.6, 11.4,7.5, 4.1 Hz, 1H), ¹⁹F NMR (376 0.48 (dtd, J = 12.9, 7.5, 3.5 MHz, Hz,1H) Benzene-d₆) δ −128.4 (d, J = 155.5 Hz), −143.9 (d, J = 155.6 Hz)FA50

Colorless oil (400 MHz, Benzene-d₆) δ 8.66 (d, J = 2.7 Hz, 1H), 8.29(dd, J = 4.7, 1.5 Hz, 1H), 7.53 (ddd, J = 8.3, 2.7, 1.5 Hz, 1H), 6.86(s, 1H), 6.67-6.48 (m, 1H), 3.99- 3.85 (m, 2H), 3.56 (q, J = 7.2 Hz,2H), 2.74 (t, J = 7.7 ¹³C NMR (101 MHz, Benzene-d₆) δ 171.2, 156.8,148.4, 140.9, 139.6, 135.6, 126.0, 125.4, 124.3, 123.7, Hz, 2H), 2.34(t, J = 7.5 Hz, 72.0, 44.1, 2H), 1.76 (s, 3H), 1.61 (qd, 34.9, 30.3, J =16.1, 14.5, 7.7 Hz, 1H), 26.9, 25.5, 1.50-1.36 (m, 1H), 1.23 20.2, 20.0(t, (ddq, J = 14.7, 11.3, 7.4 Hz, J = 11.0 Hz), 1H), 0.97 (t, J = 7.2Hz, 3H), 15.6 (t, J = 0.94-0.78 (m, 1H), 0.44 10.9 Hz), 13.3 (dtd, J =12.8, 7.5, 3.5 Hz, ¹⁹F NMR (376 1H) MHz, Benzene-d₆) δ −128.3 (d, J =155.4 Hz), −143.8 (d, J = 155.5 Hz) FA51

Colorless oil ESIMS 335 ([M + H]⁺) (400 MHz, CDCl₃) δ 9.02 (t, J = 2.1Hz, 1H), 8.61 (dq, J = 4.6, 1.4 Hz, 1H), 8.33 (s, 1H), 8.05 (ddd, J =8.4, 2.7, 1.5 Hz, 1H), 7.45 (ddd, J = 8.4, 4.7, 1.6 Hz, 1H), 4.00 (s,1H), 3.35 (s, 1H), 3.14 (ddd, J = 18.3, 10.5, 2.2 Hz, 1H), 3.02-2.84 (m,1H), 2.37 (ddd, J = 18.3, ¹³C NMR (101 MHz, CDCl₃) δ 208.0, 176.5,148.4, 140.6, 140.2, 136.1, 135.7, 126.1, 124.0, 123.8, 48.2, 43.3,32.0, 29.8, 3.5, 1.5 Hz, 1H), 2.13 (s, 17.6, 12.7 3H), 1.15 (td, J =7.2, 2.1 Hz, 3H), 1.06 (dd, J = 7.0, 2.0 Hz, 3H) FA52

Colorless oil ESIMS 350 ([M + H]⁺) (400 MHz, CDCl₃) δ 9.45 (s, 1H), 8.88(d, J = 2.6 Hz, 1H), 8.39 (d, J = 4.8 Hz, 1H), 8.18-7.97 (m, 2H), 7.33(dd, J = 8.1, 5.2 Hz, 1H), 3.93 (s, 1H), 3.48 (s, 1H), 3.07 (dp, J =8.6, 6.6 Hz, 1H), 2.52 (dd, J = 12.3, 6.1 Hz, 1H), 2.41 (dd, J = 12.3,8.8 Hz, 1H), 1.84 (s, 3H), ¹³C NMR (101 MHz,CDCl₃) δ 176.2, 157.4,147.8, 140.8, 139.7, 135.9, 127.6, 126.5, 124.1, 123.6, 43.4, 34.4,33.1, 21.8, 18.5, 13.1 1.22-1.07 (m, 6H) FA53

Colorless oil ESIMS 350 ([M + H]⁺) (400 MHz, CDCl₃) δ 9.48 (s, 1H), 8.96(d, J = 2.7 Hz, 1H), 8.56 (dd, J = 4.8, 1.4 Hz, 1H), 8.18 (s, 1H), 8.12(ddd, J = 8.4, 2.8, 1.5 Hz, 1H), 7.43 (dd, J = 8.4, 4.8 Hz, 1H),3.94-3.75 (m, 1H), 3.68-3.36 (m, 1H), 2.94- 2.73 (m, 1H), 2.65 (dd, J =15.1, 9.8 Hz, 1H), 2.24-2.10 (m, 1H), 1.79 (s, 3H), 1.11 ¹³C NMR (101MHz, CDCl₃) δ176.63, 156.5, 148.0, 140.9, 139.6, 135.9, 127.4, 126.5,124.3, 124.0, 43.5, 40.3, 34.6, 18.5, 14.6, 12.9 (dt, J = 7.2, 3.7 Hz,6H) FA54

Colorless oil ESIMS 336 ([M + H]⁺) (400 MHz, Acetone-d₆) δ 9.09 (dd, J =2.8, 0.8 Hz, 1H), 8.73 (s, 1H), 8.60 (dd, J = 4.8, 1.5 Hz, 1H), 8.22(ddd, J = 8.3, 2.7, 1.4 Hz, 1H), 7.57 (ddd, J = 8.3, 4.7, 0.8 Hz, 1H),7.42-7.13 (m, 1H), 3.85-3.65 (m, 1H), 3.55 (s, 2H), 2.83-2.67 (m, 1H),2.45 (ddd, J = 14.9, 8.1, 5.3 Hz, 1H), 2.21-2.08 (m, 1H), ¹³C NMR (101MHz, Acetone-d₆) δ 210.0, 175.9, 149.1, 149.0, 148.9, 140.9, 140.9,136.8, 129.4, 126.7, 125.0, 124.6, 44.2, 18.2, 13.3 1.12 (t, J = 7.1 Hz,3H), 1.06 (d, J = 6.8 Hz, 3H) FA55

Colorless oil ESIMS 337 ([M + H]⁺) (400 MHz, Acetone-d₆) δ 9.10 (d, J =2.8 Hz, 1H), 8.80 (s, 1H), 8.59 (dd, J = 4.7, 1.5 Hz, 1H), 8.23 (ddd, J= 8.4, 2.7, 1.4 Hz, 1H), 7.69-7.52 (m, 1H), 6.62 (dd, J = 5.7, 4.9 Hz,1H), 3.76 (s, 3H), 2.89-2.66 (m, 1H), 2.61-2.37 (m, 2H), 1.14 (t, J =7.1 Hz, 3H), 1.08 (d, J = ¹³C NMR (101 MHz, Acetone-d₆) δ 209.9, 206.1,176.0, 149.2, 149.1, 149.1, 141.0, 141.0, 140.8, 127.7, 126.7, 126.6,124.9, 44.3, 6.8 Hz, 3H) 17.4, 13.3 FA56

Colorless oil ESIMS 322 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.95 (dt, J = 2.8,0.9 Hz, 1H), 8.61 (dd, J = 4.8, 1.4 Hz, 1H), 8.17-7.94 (m, 3H), 7.46(ddd, J = 8.3, 4.6, 1.2 Hz, 2H), 6.80 (t, J = 5.5 Hz, 1H), 3.71 (qd, J =7.2, 1.9 Hz, 2H), 3.48 (q, J = 7.0 Hz, 1H), 2.65 (td, J = 7.2, 5.5 Hz,1H), 2.53 (td, J = 7.1, 5.2 Hz, 1H), 2.37 (td, J = ¹³C NMR (101 MHz,CDCl₃) δ 171.7, 151.2, 150.8, 148.5, 139.9, 135.7, 126.5, 126.3, 124.2,124.0, 44.0, 30.6, 25.2, 13.1 7.3, 2.7 Hz, 2H) FA57

Colorless oil ESIMS 454 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.95 (t, J = 2.6Hz, 1H), 8.62 (dd, J = 4.7, 1.5 Hz, 1H), 8.08- 8.00 (m, 2H), 7.46 (dd, J= 8.3, 4.7 Hz, 1H), 4.14-4.03 (m, 2H), 3.92 (s, 1H), 3.49 (s, 1H), 2.82(p, J = 6.2 Hz, 1H), 2.63 (ddd, J = 15.0, 8.8, 6.0 Hz, 1H), 2.23-2.10(m, 1H), 1.77 (s, 4H), 1.57 ¹⁹F NMR (376 MHz, CDCl₃) δ −128.46, −128.47,−128.87, −128.88, −143.76, −144.17 (ddtt, J = 18.6, 11.4, 7.4, 3.6 Hz,1H), 1.46-1.34 (m, 1H), 1.26 (s, 1H), 1.15 (td, J = 7.2, 1.1 Hz, 3H),1.09 (d, J = 6.8 Hz, 3H), 0.99- 0.86 (m, 1H) FA58

Colorless oil ESIMS 454 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.97 (d, J = 2.6Hz, 1H), 8.62 (dd, J = 4.8, 1.4 Hz, 1H), 8.11- 7.99 (m, 1H), 7.88 (s,1H), 7.51-7.40 (m, 1H), 3.97- 3.50 (m, 4H), 2.94-2.85 (m, 2H), 2.51 (dd,J = 12.4, 6.2 Hz, 1H), 2.38 (t, J = 10.5 ¹⁹F NMR (376 MHz, CDCl₃) δ−128.58, −128.66, −129.00, −129.08, −143.70, −143.89, Hz, 1H), 1.83 (d,J = 1.6 Hz, −144.11, 3H), 1.56 (s, 2H), 1.43-1.19 −144.30 (m, 1H), 1.15(t, J = 7.2 Hz, 3H), 1.11 (d, J = 6.9 Hz, 3H), 0.86-0.69 (m, 1H) FA59

Colorless oil ESIMS 440 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.95 (d, J = 2.7Hz, 1H), 8.63 (dd, J = 4.7, 1.4 Hz, 1H), 8.10- 8.00 (m, 2H), 7.46 (ddd,J = 8.3, 4.8, 0.8 Hz, 1H), 7.40- 7.32 (m, 1H), 4.16-4.02 (m, 2H), 3.85(s, 1H), 3.55 (s, 1H), 2.70 (d, J = 10.2 Hz, 1H), 2.56 (dddd, J = 14.2,8.9, 5.3, 3.8 Hz, 1H), 2.27- ¹⁹F NMR (376 MHz, CDCl₃) δ −128.46,−128.87, −143.81, −144.22 2.11 (m, 1H), 1.95-1.65 (m, 2H), 1.63-1.50 (m,1H), 1.39 (dddd, J = 12.6, 11.5, 7.5, 4.1 Hz, 1H), 1.18-1.11 (m, 6H),1.00-0.80 (m, 1H) FA60

Colorless oil ESIMS 441 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.95 (t, J = 2.8Hz, 1H), 8.63 (dt, J = 4.7, 1.4 Hz, 1H), 8.04 (ddd, J = 7.3, 2.1, 1.0Hz, 1H), 7.51-7.43 (m, 1H), 7.36 (dd, J = 6.5, 5.4 Hz, 1H), 4.06 (t, J =6.3 Hz, 2H), 3.96-3.40 (m, 4H), ¹⁹F NMR (376 MHz, CDCl₃) δ −128.46,−128.87, −143.81, −144.22 2.75-2.63 (m, 1H), 2.62- 2.40 (m, 1H),2.29-2.12 (m, 1H), 1.90-1.64 (m, 1H), 1.57-1.45 (m, 1H), 1.45- 1.21 (m,1H), 1.15 (q, J = 7.1 Hz, 6H), 1.00-0.79 (m, 1H) FA61

Colorless oil ESIMS 426 ([M + H]⁺) (400 MHz, CDCl₃) δ 9.05- 8.86 (m,1H), 8.63 (dd, J = 4.8, 1.5 Hz, 1H), 8.05 (ddd, J = 8.3, 2.8, 1.5 Hz,1H), 7.95 (s, 1H), 7.51-7.37 (m, 2H), 6.72 (t, J = 5.4 Hz, 1H),4.15-4.07 (m, 1H), 4.04 (t, J = 6.3 Hz, 1H), 3.71 (q, J = 7.2 Hz, 2H),2.61 (td, J = 7.2, 5.4 Hz, 1H), 2.56-2.46 ¹⁹F NMR (376 MHz, CDCl₃) δ−128.44, −128.45, −128.86, −128.86, −143.75, −143.92, −144.17, −144.34(m, 1H), 2.35 (q, J = 7.4 Hz, 2H), 1.89-1.65 (m, 1H), 1.55 (dddd, J =18.7, 14.4, 7.2, 4.0 Hz, 1H), 1.38 (dddd, J = 12.6, 11.3, 7.5, 4.0 Hz,1H), 1.16 (t, J = 7.2 Hz, 3H), 0.91 (ddq, J = 12.9, 7.5, 3.6 Hz, 1H)FA62

Colorless oil ESIMS 467 ([M + H]⁺) (400 MHz, CDCl₃) δ 9.00 (dd, J = 2.6,1.2 Hz, 1H), 8.61 (dt, J = 4.7, 1.5 Hz, 1H), 8.10-8.03 (m, 2H), 7.45(dd, J = 8.3, 4.7 Hz, 1H), 3.85-3.54 (m, 2H), 3.45-3.16 (m, 4H), 2.37(tt, J = 16.0, 8.3 Hz, 3H), 2.26-2.18 (m, ¹⁹F NMR (376 MHz, CDCl₃) δ−128.49, −128.58, −128.91, −128.99, −143.43, −143.62, 1H), 1.99 (dtd, J= 14.1, 7.1, −143.85, 4.1 Hz, 1H), 1.82 (dt, J = −144.04 14.1, 7.3 Hz,1H), 1.73-1.58 (m, 3H), 1.49-1.30 (m, 2H), 1.14 (td, J = 7.2, 1.3 Hz,3H), 0.95-0.81 (m, 1H) FA63

White semi- solid ESIMS 348 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.95 (dd, J =2.7, 0.7 Hz, 1H), 8.62 (dd, J = 4.8, 1.5 Hz, 1H), 8.03 (ddd, J = 8.3,2.7, 1.4 Hz, 1H), 7.99 (s, 1H), 7.45 (ddd, J = 8.3, 4.8, 0.8 Hz, 1H),5.69 (s, 1H), 3.71 (ddt, J = 38.0, 13.6, 7.4 Hz, 2H), 3.41-3.29 (m, 2H),2.88 (qd, J = 9.4, 3.7 Hz, 1H), 2.73 (dd, J = 16.8, 3.7 Hz, 1H), 2.73(dd, J = 16.8, 3.7 ¹³C NMR (101 MHz, CDCl₃) δ 179.13, 171.3, 148.6,140.8, 140.1, 135.6, 126.6, 126.3, 124.1, 123.8, 43.9, 40.2, 37.6, 35.5,29.3, 13.1 Hz, 1H), 2.53 (dddd, J = 12.3, 9.0, 6.0, 3.3 Hz, 1H),2.29-2.18 (m, 1H), 1.82 (dq, J = 12.7, 9.3 Hz, 1H), 1.16 (t, J = 7.2 Hz,3H) FA64

Colorless oil ESIMS 452 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.96 (td, J = 2.9,0.7 Hz, 1H), 8.61 (dt, J = 4.7, 1.4 Hz, 1H), 8.14-8.01 (m, 2H), 7.45(dddd, J = 8.3, 4.8, 1.5, 0.8 Hz, 1H), 3.76 (dt, J = 14.1, 7.0 Hz, 1H),3.64 (dqd, J = 14.2, 7.2, 2.2 Hz, 1H), 3.50-3.19 (m, 4H), 2.94 (qt, J =9.2, 3.4 Hz, 1H), 2.73 (dd, J = 16.8, 3.9 Hz, 1H), 2.50-2.37 (m, 1H),1.80- 1.58 (m, 4H), 1.56-1.29 (m, 2H), 1.16 (td, J = 7.1, 0.9 ¹⁹F NMR(376 MHz, CDCl₃) δ −128.54, −128.71, −128.96, −129.12, −143.41, −143.59,−143.82, −144.00 Hz, 3H), 1.00-0.81 (m, 1H) FA65

Colorless oil ESIMS 430 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.96 (dd, J = 2.7,0.7 Hz, 1H), 8.62 (dd, J = 4.8, 1.5 Hz, 1H), 8.09-8.01 (m, 2H), 7.46(ddd, J = 8.3, 4.8, 0.8 Hz, 1H), 4.02-3.85 (m, 1H), 3.86-3.71 (m, 2H),3.64 (dq, J = 14.0, 7.1 Hz, 1H), 3.48 (ddd, J = 11.3, 9.1, 6.8 Hz, 2H),2.96 (qd, J = 9.2, 3.8 Hz, 1H), 2.73 (dd, J = 16.8, 3.9 Hz, 1H), 2.48(dddd, J = 15.7, 9.2, 6.9, 2.6 Hz, 1H), 2.26 (dd, J = 16.9, 8.9 Hz, 1H),1.79 (dq, J = 11.9, 9.3 Hz, 1H), 1.16 (t, J = 7.2 ¹⁹F NMR (376 MHz,CDCl₃) δ −69.9 Hz, 3H) FA66

Yellow oil ESIMS 307 ([M + H]⁺) (400 MHz, CDCl₃) δ 9.03- 8.87 (m, 1H),8.62 (dt, J = 4.0, 2.0 Hz, 1H), 8.04-7.99 (m, 2H), 7.51-7.39 (m, 1H),3.73 (d, J = 7.5 Hz, 2H), 3.40 (s, 2H), 2.18 (s, 3H), 1.18 (t, J = 7.2Hz, 3H) IR (thin film) 1658 cm⁻¹ FA67

Colorless oil ESIMS 417 ([M + H]⁺) (400 MHz, CDCl₃) δ 9.00 (dd, J = 2.7,0.8 Hz, 1H), 8.62 (dd, J = 4.8, 1.4 Hz, 1H), 8.16 (s, 1H), 8.06 (ddd, J= 8.3. 2.7, 1.4 Hz, 1H), 7.45 (ddd, J = 8.3, 4.8, 0.8 Hz, 1H), 5.79(ddt, J = 16.9, 10.2, 6.6 Hz, 1H), 5.08-4.88 (m, 2H), 3.73-3.62 (m, 2H),3.56-3.50 (m, 2H), ¹³C NMR (101 MHz, CDCl₃) δ 176.91, 170.9, 148.6,140.6, 140.3, 137.9, 135.6, 127.1, 126.3, 124.0, 123.6, 115.1, 46.1,43.9, 41.2, 3.42-3.34 (m, 2H), 2.50-2.29 39.1, 32.6, (m, 3H), 2.16-2.02(m, 3H), 31.3, 30.5, 1.94 (dddd, J = 13.7, 9.5, 25.2, 13.0 6.9, 4.3 Hz,1H), 1.64 (dq, J = 12.6, 8.6 Hz, 1H), 1.48- 1.31 (m, 1H), 1.14 (t, J =7.2 Hz, 3H) FA68

Light brown oil ESIMS 387 ([M + H]⁺) (400 MHz, DMSO-d₆) δ 9.06 (dd, J =2.7, 0.7 Hz, 1H), 8.88 (s, 1H), 8.59 (dd, J = 4.7, 1.4 Hz, 1H), 8.21(ddd, J = 8.3, 2.7, 1.4 Hz, 1H), 7.81 (d, J = 2.4 Hz, 1H), 7.59 (ddd, J= 8.4, 4.7, 0.7 Hz, 1H), 6.64 (d, J = 2.4 Hz, 1H), 4.41 (t, J = 6.6 Hz,2H), 3.57 (d, J = 7.5 Hz, 2H), 2.72 (t, J = 6.7 Hz, 2H), 2.39 (s, 3H),1.05 (t, J = 7.1 Hz, 3H) IR (thin film) 3106, 2974, 1665 cm⁻¹ FA69

Colorless oil EIMS 286 ([M]⁺) (400 MHz, Acetone-d₆) δ 9.09 (d, J = 2.5Hz, 1H), 8.51 (dd, J = 5.3, 2.0 Hz, 2H), 8.19 (ddd, J = 8.3, 2.7, 1.5Hz, 1H), 7.51 (ddd, J = 8.3, 4.7, 0.7 Hz, 1H), 3.14 (s, 3H), 2.71-2.63(m, 2H), 2.36-2.30 (m, 2H), 2.28 (s, 3H), 2.09 (s, 3H) ¹³C NMR (101 MHz,CDCl₃) δ 207.75, 172.6, 150.0, 141.3, 138.0, 134.8, 130.2, 128.7, 126.1,125.5, 38.3, 37.1, 30.0, 27.6, 11.1 FA70

Colorless oil EIMS 332 ([M]⁺) (400 MHz, CDCl₃) δ 8.77 (s, 1H), 8.42 (d,J = 2.5 Hz, 1H), 7.90 (s, 1H), 7.86 (dt, J = 9.4, 2.3 Hz, 1H), 3.66 (s,2H), 2.48 (t, J = 6.9 Hz, 2H), 2.24 (s, 3H), 2.10 (s, 5H), 1.85 (p, J =7.0 Hz, 2H), 1.13 (t, J = 7.2 Hz, 3H) ¹⁹F NMR (376 MHz, CDCl₃) δ −121.0FA71

Tan solid 85-86° C. EIMS 330 ([M]⁺) (400 MHz, CDCl₃) δ 8.96 (s, 1H),8.46 (s, 1H), 8.10 (s, 1H), 8.02 (d, J = 9.2 Hz, 1H), 3.69 (s, 2H), 3.03(p, J = 8.2 Hz, 1H), 2.56 (dd, J = 18.1, 9.0 Hz, 1H), 2.41 (m, 1H), 2.27(s, 3H), 2.11 (m, 4H), 1.15 (t, J = 7.2 Hz, 3H) ¹⁹F NMR (376 MHz, CDCl₃)δ −121.3 FA72

White solid 117-120° C. ESIMS 323 ([M + H]⁺) (400 MHz, CDCl₃) δ 9.36 (s,1H), 8.69 (d, J = 3.9 Hz, 1H), 8.46 (s, 1H), 8.40 (d, J = 8.4 Hz, 1H),7.71 (dd, J = 8.2, 5.1 Hz, 1H), 4.50 (s, 2H), 3.72 (q, J = 7.1 Hz, 2H),2.14 (s, 3H), 1.18 (t, J = 7.2 Hz, 3H) FA73

Off-white solid 73-75° C. ESIMS 352 ([M + H]⁺) (400 MHz, CDCl₃) δ 9.01(s, 1H), 8.57 (s, 1H), 8.16 (d, J = 8.1 Hz, 1H), 8.02 (s, 1H), 7.51 (dd,J = 8.2, 4.8 Hz, 1H), 3.72 (s, 2H), 1.52 (s, 9H), 1.08 (t, J = 7.1 Hz,3H) FA74

Yellow oil ESIMS 405 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.99 (d, J = 2.5 Hz,1H), 8.64 (dd, J = 4.7, 1.3 Hz, 1H), 8.17 (s, 1H), 8.03 (ddd, J = 8.3,2.7, 1.4 Hz, 1H), 7.46 (dd, J = 8.3, 4.8 Hz, 1H), 5.11 (q, J = 6.5 Hz,1H), 3.69 (d, J = 227.6 Hz, 2H), 3.27 (m, 2H), 1.42 (d, J = 6.8 Hz, 3H),1.17 (t, J = 7.2 Hz, 3H) ¹⁹F NMR (376 MHz, CDCl₃) δ −63.5 FA75

Brown solid 96-97° C. ESIMS 307 ([M + H]⁺) (400 MHz, CDCl₃) δ 8.95 (d, J= 2.6 Hz, 1H), 8.61 (dd, J = 4.7, 1.4 Hz, 1H), 8.11 (s, 1H), 8.02 (ddd,J = 8.3, 2.7, 1.4 Hz, 1H), 7.44 (ddd, J = 8.3, 4.8, 0.6 Hz, 1H), 3.21(s, 3H), 2.78 (t, J = 6.3 Hz, 2H), 2.41 (t, J = 6.3 Hz, 2H), 2.18 (s,3H) FA76

Brown viscous oil HRMS-ESI [M + H]⁺ calcd for C₁₇H₁₉ClF₃N₄O₂, 403.1143;found, 403.1149 (400 MHz, CDCl₃) δ 8.97 (d, J = 2.7 Hz, 1H), 8.63 (dd, J= 4.7, 1.4 Hz, 1H), 8.10- 8.01 (multiple peaks, 2H), 7.46 (ddd, J = 8.3,4.8, 0.7 Hz, 1H), 3.68 (q, J = 7.2 Hz, 2H), 2.84-2.70 (multiple peaks,4H), 2.51-2.34 (multiple peaks, 4H), 1.15 (t, J = 7.2 Hz, 3H) ¹⁹F NMR(376 MHz, CDCl₃) δ −66.6 IR (thin film) 1721, 1665 cm⁻¹ FA77

Orange oil HRMS-ESI [M + H]⁺ calcd for C₂₀H₂₃ClN₅O₃, 416.1484; found,416.1489 (400 MHz, CDCl₃) δ 8.97 (dt, J = 2.0, 0.9 Hz, 1H), 8.61 (dt, J= 4.8, 1.6 Hz, 1H), 8.11 (s, 1H), 8.03 (ddt, J = 8.3, 2.6, 1.2 Hz, 1H),7.44 (dddd, J = 8.4, 4.8, 1.7, 0.8 Hz, 1H), 7.34 (ddd, J = 9.8, 1.9, 0.8Hz, 1H), 6.31 (ddd, J = 9.4, 3.2, 1.9 Hz, 1H), 6.22 (ddd, J = 11.4, 3.20.9 Hz, 1H), 4.51 (d, J = IR (thin film) 3090, 1648 cm⁻¹ 20.2 Hz, 2H),3.72 (qd, J = 7.1, 3.1 Hz, 2H), 3.03 (s, 1.7H, major), 2.92 (s, 1.3H,minor), 2.87-2.78 (m, 0.9H, minor), 2.73-2.64 (m, 1.1H, major), 2.51 (brs, 2H), 1.16 (td, J = 7.2, 1.7 Hz, 3H)

TABLE 4 Prepared accord- ing to No. Structure Example: C1

3 C2

6 C3

12 C4

12 C5

12 C6

16 C7

18 C8

22 C9

24 C10

24 C11

24 C12

27 C13

28 C14

36 CA1

1 CA2

24 CA3

41

TABLE 5 May be prepared according No. Formula to example P1

PE1 P2

PE1 P3

PE1 P4

PE1 P5

PE1 P6

PE1 P7

PE1 P8

PE2 P10

PE2 P11

PE2 P12

PE2 P13

PE2 P14

PE2 P15

PE2 P16

PE3 P17

PE3 P18

PE2 P19

PE2 P20

PE3 P21

PE3 P22

PE3 P23

PE3 P24

PE3 P25

PE3 P26

PE4 P27

PE4 P28

PE3 P29

PE3 P30

PE3 P31

PE3 P32

PE3 P33

PE3 P34

PE4 P35

PE4 P36

PE4 P37

PE4 P38

PE5 P39

PE5

We claim:
 1. A process comprising applying a pesticidal composition toan area to control a pest, in an amount sufficient to control such pest,wherein the pesticidal composition comprises a compound of formula I orany agriculturally acceptable salt thereof:

wherein: (a) R₁, R₂, and R₄ are independently selected from hydrogen, F,Cl, Br, I, substituted or unsubstituted C₁-C₆ alkyl, or substituted orunsubstituted C₁-C₆ haloalkyl, wherein each said R₁, R₂, and R₄, whensubstituted, has one or more substituents selected from F, Cl, Br, I,CN, NO₂, C₁-C₆ alkyl, C₂-C₆ alkenyl, C₁-C₆ haloalkyl, C₃-C₁₀ cycloalkyl,or C₃-C₁₀ halocycloalkyl, (each of which that may be substituted, mayoptionally be substituted with R₁₀); (b) R₃ is selected from hydrogen,F, Cl, Br, I, CN, NO₂, substituted or unsubstituted C₁-C₆ alkyl,substituted or unsubstituted C₂-C₆ alkenyl, substituted or unsubstitutedC₁-C₆ alkoxy, substituted or unsubstituted C₃-C₁₀ cycloalkyl,substituted or unsubstituted C₁-C₆ haloalkyl, substituted orunsubstituted C₆-C₂₀ aryl, substituted or unsubstituted C₁-C₂₀heterocyclyl, OR₁₀, C(═X₁)R₁₀, C(═X₁)OR₁₀, C(═X₁)N(R₁₀)₂, N(R₁₀)₂,N(R₁₀)C(═X₁)R₁₀, SR₁₀, S(O)_(n)OR₁₀, or R₁₀S(O)_(n)R₁₀, wherein eachsaid R₃, when substituted, has one or more substituents selected from F,Cl, Br, I, CN, NO₂, C₁-C₆ alkyl, C₂-C₆ alkenyl, C₁-C₆ haloalkyl, C₂-C₆haloalkenyl, C₁-C₆ haloalkyloxy, C₂-C₆ haloalkenyloxy, C₃-C₁₀cycloalkyl, C₃-C₁₀ cycloalkenyl, C₃-C₁₀ halocycloalkyl, C₃-C₁₀halocycloalkenyl, OR₁₀, S(O)_(n)OR₁₀, C₆-C₂₀ aryl, or C₁-C₂₀heterocyclyl, (each of which that may be substituted, may optionally besubstituted with R₁₀); (c) R₅ is selected from H, F, Cl, Br, I, CN, NO₂,substituted or unsubstituted C₁-C₆ alkyl, substituted or unsubstitutedC₂-C₆ alkenyl, substituted or unsubstituted C₁-C₆ alkoxy, C₃-C₁₀cycloalkyl, substituted or unsubstituted C₆-C₂₀ aryl, substituted orunsubstituted C₁-C₂₀ heterocyclyl, OR₁₀, C(═X₁)R₁₀, C(═X₁)OR₁₀,C(═X₁)N(R₁₀)₂, N(R₁₀)₂, N(R₁₀)C(═X₁)R₁₀, SR₁₀, S(O)_(n)OR₁₀, orR₁₀S(O)_(n)R₁₀, wherein each said R₅, when substituted, has one or moresubstituents selected from F, Cl, Br, I, CN, NO₂, C₁-C₆ alkyl, C₂-C₆alkenyl, C₁-C₆ haloalkyl, C₂-C₆ haloalkenyl, C₁-C₆ haloalkyloxy, C₂-C₆haloalkenyloxy, C₃-C₁₀ cycloalkyl, C₃-C₁₀ cycloalkenyl, C₃-C₁₀halocycloalkyl, C₃-C₁₀ halocycloalkenyl, OR₁₀, S(O)_(n)OR₁₀, C₆-C₂₀aryl, or C₁-C₂₀ heterocyclyl, (each of which that may be substituted,may optionally be substituted with R₁₀); (d) R₆ is H, F, Cl, Br, I,substituted or unsubstituted C₁-C₆ alkyl, or C₁-C₆ haloalkyl, whereineach said R₆, when substituted, has one or more substituents selectedfrom F, Cl, Br, I, CN, NO₂, C₁-C₆ alkyl, C₂-C₆ alkenyl, C₁-C₆ haloalkyl,C₂-C₆ haloalkenyl, C₁-C₆ haloalkyloxy, C₂-C₆ haloalkenyloxy, C₃-C₁₀cycloalkyl, C₃-C₁₀ cycloalkenyl, C₃-C₁₀ halocycloalkyl, or C₃-C₁₀halocycloalkenyl; (e) R₇ is selected from hydrogen, substituted orunsubstituted C₁-C₆ alkyl, substituted or unsubstituted C₂-C₆ alkenyl,substituted or unsubstituted C₂-C₆ alkynyl, substituted or unsubstitutedC₁-C₆ alkoxy, substituted or unsubstituted C₃-C₁₀ cycloalkyl, C₁-C₆alkyl C₂-C₆ alkynyl wherein the alkyl and alkynyl is independentlysubstituted or unsubstituted, substituted or unsubstituted C₆-C₂₀ aryl,substituted or unsubstituted C₁-C₂₀ heterocyclyl, C₁-C₆ alkyl C₆-C₂₀aryl wherein the alkyl and aryl is independently substituted orunsubstituted), C₁-C₆ alkyl-(C₃-C₁₀ cyclohaloalkyl) wherein the alkyland cyclohaloalkyl is independently substituted or unsubstituted, orC₁-C₆ alkyl-(C₃-C₁₀ cycloalkyl) wherein the alkyl and cycloalkyl isindependently substituted or unsubstituted, wherein each said R₇, whensubstituted, has one or more substituents selected from F, Cl, Br, I,CN, NO₂, C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl C₁-C₆ haloalkyl,C₂-C₆ haloalkenyl, C₁-C₆ haloalkyloxy, C₂-C₆ haloalkenyloxy, C₃-C₁₀cycloalkyl, C₃-C₁₀ cycloalkenyl, C₃-C₁₀ halocycloalkyl, C₃-C₁₀halocycloalkenyl, OR₁₀, S(O)_(n)OR₁₀, C₆-C₂₀ aryl, or C₁-C₂₀heterocyclyl, R₁₀ aryl, (each of which that may be substituted, mayoptionally be substituted with R₁₀); (f) R₈ is selected from substitutedor unsubstituted C₁-C₆ alkyl, substituted or unsubstituted C₂-C₆alkenyl, substituted or unsubstituted C₁-C₆ alkoxy, substituted orunsubstituted C₃-C₁₀ cycloalkyl, substituted or unsubstituted C₃-C₁₀halocycloalkyl substituted or unsubstituted C₃-C₁₀ cycloalkenyl,substituted or unsubstituted C₆-C₂₀ aryl, or substituted orunsubstituted C₁-C₂₀ heterocyclyl, wherein each said R₈, whensubstituted, has one or more substituents selected from F, Cl, Br, I,CN, NO₂, substituted or unsubstituted C₁-C₆ alkyl, substituted orunsubstituted C₂-C₆ alkenyl, substituted or unsubstituted C₁-C₆haloalkyl, substituted or unsubstituted C₂-C₆ haloalkenyl, substitutedor unsubstituted C₁-C₆ haloalkyloxy, substituted or unsubstituted C₂-C₆haloalkenyloxy, substituted or unsubstituted C₃-C₁₀ cycloalkyl,substituted or unsubstituted C₃-C₁₀ cycloalkenyl, substituted orunsubstituted C₃-C₁₀ halocycloalkyl, substituted or unsubstituted C₃-C₁₀halocycloalkenyl, oxo, OR₁₀, S(O)_(n)R₁₀, substituted or unsubstitutedC₆-C₂₀ aryl, or substituted or unsubstituted C₁-C₂₀ heterocyclyl, (eachof which, when substituted, is substituted with R₁₀); (g) L is N(R₉);(h) L_(a) is selected from R₉, OR₉, N(R₉)₂, N(R₉)(R₁₁), N(R₉)(OR₁₁),NR₉)C(═X₁)R₉, N(R₉)C(═X₁)(R₁₁), C(R₉)₃, C(R₉)(R₁₁)(R₁₂), or SR₉;optionally L and L_(a) are connected in a cyclic arrangement, whichforms 3-8 membered heterocycles or carbocycles including L and L_(a),wherein the cyclic arrangement contains none or at least one of O, S, orN heteroatoms, and the cyclic arrangement is unsubstituted orsubstituted, wherein, when substituted, the cyclic arrangement has oneor more substituents selected from F, Cl, Br, I, CN, NO₂, substituted orunsubstituted C₁-C₆ alkyl, substituted or unsubstituted C₂-C₆ alkenyl,substituted or unsubstituted C₂-C₆ alkynyl, substituted or unsubstitutedC₁-C₆ haloalkyl, substituted or unsubstituted C₂-C₆ haloalkenyl,substituted or unsubstituted C₁-C₆ haloalkyloxy, substituted orunsubstituted C₂-C₆ haloalkenyloxy, substituted or unsubstituted C₃-C₁₀cycloalkyl, substituted or unsubstituted C₃-C₁₀ cycloalkenyl,substituted or unsubstituted C₃-C₁₀ halocycloalkyl, substituted orunsubstituted C₃-C₁₀ halocycloalkenyl, N(R₉)S(O)_(n)R₁₁, oxo, OR₉,S(O)_(n)OR₉, R₉S(O)_(n)R₁₁, S(O)_(n)R₉, substituted or unsubstitutedC₆-C₂₀ aryl, or substituted or unsubstituted C₁-C₂₀ heterocyclyl (eachof which, when substituted, is substituted with R₁₀); (i) R₉, R₁₁, R₁₂,and R₁₃ are independently selected from hydrogen, CN, NO₂, substitutedor unsubstituted C₁-C₆ alkyl, substituted or unsubstituted C₂-C₆alkenyl, substituted or unsubstituted C₁-C₆ alkoxy, substituted orunsubstituted C₃-C₁₀ cycloalkyl, substituted or unsubstituted C₃-C₁₀halocycloalkyl, substituted or unsubstituted C₃-C₁₀ cycloalkenyl,substituted or unsubstituted C₆-C₂₀ aryl, or substituted orunsubstituted C₁-C₂₀ heterocyclyl, wherein each of said R₉, R₁₁, andR₁₂, when substituted, has one or more substituents selected from F, Cl,Br, I, CN, NO₂, substituted or unsubstituted C₁-C₆ alkyl, substituted orunsubstituted C₂-C₆ alkenyl, substituted or unsubstituted C₁-C₆haloalkyl, substituted or unsubstituted C₂-C₆ haloalkenyl, substitutedor unsubstituted C₁-C₆ haloalkyloxy, substituted or unsubstituted C₂-C₆haloalkenyloxy, substituted or unsubstituted C₃-C₁₀ cycloalkyl,substituted or unsubstituted C₃-C₁₀ cycloalkenyl, substituted orunsubstituted C₃-C₁₀ halocycloalkyl, substituted or unsubstituted C₃-C₁₀halocycloalkenyl, oxo, OR₁₀, C(═X₁)R₁₀, S(O)_(n)R₁₀, substituted orunsubstituted C₆-C₂₀ aryl, or substituted or unsubstituted C₁-C₂₀heterocyclyl, (each of which, when substituted, is substituted withR₁₀); (j) R₁₀ is H, F, Cl, Br, I, CN, NO₂, substituted or unsubstitutedC₁-C₆ alkyl, substituted or unsubstituted C₂-C₆ alkenyl, substituted orunsubstituted C₁-C₆ alkoxy, substituted or unsubstituted C₂-C₆alkenyloxy, substituted or unsubstituted C₃-C₁₀ cycloalkyl, substitutedor unsubstituted C₃-C₁₀ cycloalkenyl, substituted or unsubstitutedC₆-C₂₀ aryl, substituted or unsubstituted C₁-C₂₀ heterocyclyl,substituted or unsubstituted S(O)_(n)C₁-C₆ alkyl, or substituted orunsubstituted N(C₁-C₆)alkyl)₂, wherein each said R₁₀, when substituted,has one or more substituents selected from F, Cl, Br, I, CN, NO₂, C₁-C₆alkyl, C₂-C₆ alkenyl, C₁-C₆ haloalkyl, C₂-C₆ haloalkenyl, C₁-C₆haloalkyloxy, C₂-C₆ haloalkenyloxy, C₃-C₁₀ cycloalkyl, C₃-C₁₀cycloalkenyl, C₃-C₁₀ halocycloalkyl, C₃-C₁₀ halocycloalkenyl, OC₁-C₆alkyl, OC₁-C₆ haloalkyl, S(O)_(n)C₁-C₆ alkyl, S(O)_(n)OC₁-C₆ alkyl,C₆-C₂₀ aryl, or C₁-C₂₀ heterocyclyl; (k) Q is (each independently) O orS; (l) Z is (each independently) O, S, CH₂, NR_, or NOR₁₃; (m) X₁ is(each independently) O or S; (n) n is 0, 1, or 2; and (o) x is 0 or 1.2. The process of claim 1, wherein the pest is selected from beetles,earwigs, cockroaches, flies, aphids, scales, whiteflies, leafhoppers,ants, wasps, termites, moths, butterflies, lice, grasshoppers, locusts,crickets, fleas, thrips, bristletails, mites, ticks, nematodes, andsymphylans.
 3. The process of claim 1, wherein the pest is from thePhyla Nematoda or Arthropoda.
 4. The process of claim 1, wherein thepest is from the Subphyla Chelicerata, Myriapoda, or Hexapoda.
 5. Theprocess of claim 1, wherein the pest is from the Class of Arachnida,Symphyla, or Insecta.
 6. The process of claim 1, wherein the pest isfrom the Order Anoplura, Order Coleoptera, Order Dermaptera, OrderBlattaria, Order Diptera, Order Hemiptera, Order Hymenoptera, OrderIsoptera, Order Lepidoptera, Order Mallophaga, Order Orthoptera, OrderSiphonaptera, Order Thysanoptera, Order Thysanura, Order Acarina, orOrder Symphyla.
 7. The process of claim 1, wherein the pest is MYZUPE orBEMITA.
 8. The process of claim 1, comprising applying the compositionfrom about 0.01 grams per hectare to about 5000 grams per hectare. 9.The process of claim 1, comprising applying the composition from about0.1 grams per hectare to about 500 grams per hectare.
 10. The process ofclaim 1, comprising applying the composition from about 1 gram perhectare to about 50 grams per hectare.
 11. The process of claim 1,wherein the area to control a pest is an area where apples, corn,cotton, soybeans, canola, wheat, rice, sorghum, barley, oats, potatoes,oranges, alfalfa, lettuce, strawberries, tomatoes, peppers, crucifers,pears, tobacco, almonds, sugar beets, or beans, are growing, or theseeds thereof are going to be planted.
 12. The process of claim 1,wherein the pesticidal composition is applied to a genetically modifiedplant that has been genetically modified to express one or morespecialized traits.
 13. The process of claim 1, where the compositionfurther comprises ammonium sulfate.
 14. The process of claim 1, whereinthe pesticidal composition comprises at least one compound of formula IAor IB.


15. The process of claim 1, wherein the pesticidal composition furthercomprises: (a) one or more compounds having acaricidal, algicidal,avicidal, bactericidal, fungicidal, herbicidal, insecticidal,molluscicidal, nematicidal, rodenticidal, or virucidal properties; or(b) one or more compounds that are antifeedants, bird repellents,chemosterilants, herbicide safeners, insect attractants, insectrepellents, mammal repellents, mating disrupters, plant activators,plant growth regulators, or synergists; or (c) both (a) and (b).
 16. Theprocess of claim 1, wherein the pesticidal composition further comprisesone or more compounds selected from: (3-ethoxypropyl)mercury bromide,1,2-dichloropropane, 1,3-dichloropropene, 1-methylcyclopropene,1-naphthol, 2-(octylthio)ethanol, 2,3,5-tri-iodobenzoic acid, 2,3,6-TBA,2,3,6-TBA-dimethylammonium, 2,3,6-TBA-lithium, 2,3,6-TBA-potassium,2,3,6-TBA-sodium, 2,4,5-T, 2,4,5-T-2-butoxypropyl, 2,4,5-T-2-ethylhexyl,2,4,5-T-3-butoxypropyl, 2,4,5-TB, 2,4,5-T-butometyl, 2,4,5-T-butotyl,2,4,5-T-butyl, 2,4,5-T-isobutyl, 2,4,5-T-isoctyl, 2,4,5-T-isopropyl,2,4,5-T-methyl, 2,4,5-T-pentyl, 2,4,5-T-sodium,2,4,5-T-triethylammonium, 2,4,5-T-trolamine, 2,4-D,2,4-D-2-butoxypropyl, 2,4-D-2-ethylhexyl, 2,4-D-3-butoxypropyl,2,4-D-ammonium, 2,4-DB, 2,4-DB-butyl, 2,4-DB-dimethylammonium,2,4-DB-isoctyl, 2,4-DB-potassium, 2,4-DB-sodium, 2,4-D-butotyl,2,4-D-butyl, 2,4-D-diethylammonium, 2,4-D-dimethylammonium,2,4-D-diolamine, 2,4-D-dodecylammonium, 2,4-DEB, 2,4-DEP, 2,4-D-ethyl,2,4-D-heptylammonium, 2,4-D-isobutyl, 2,4-D-isoctyl, 2,4-D-isopropyl,2,4-D-isopropylammonium, 2,4-D-lithium, 2,4-D-meptyl, 2,4-D-methyl,2,4-D-octyl, 2,4-D-pentyl, 2,4-D-potassium, 2,4-D-propyl, 2,4-D-sodium,2,4-D-tefuryl, 2,4-D-tetradecylammonium, 2,4-D-triethylammonium,2,4-D-tris(2-hydroxypropyl)ammonium, 2,4-D-trolamine, 2iP,2-methoxyethylmercury chloride, 2-phenylphenol, 3,4-DA, 3,4-DB, 3,4-DP,4-aminopyridine, 4-CPA, 4-CPA-potassium, 4-CPA-sodium, 4-CPB, 4-CPP,4-hydroxyphenethyl alcohol, 8-hydroxyquinoline sulfate,8-phenylmercurioxyquinoline, abamectin, abscisic acid, ACC, acephate,acequinocyl, acetamiprid, acethion, acetochlor, acetophos, acetoprole,acibenzolar, acibenzolar-S-methyl, acifluorfen, acifluorfen-methyl,acifluorfen-sodium, aclonifen, acrep, acrinathrin, acrolein,acrylonitrile, acypetacs, acypetacs-copper, acypetacs-zinc, alachlor,alanycarb, albendazole, aldimorph, aldoxycarb, aldrin, allethrin,allicin, allidochlor, allosamidin, alloxydim, alloxydim-sodium, allylalcohol, allyxycarb, alorac, alpha-cypermethrin, alpha-endosulfan,ametoctradin, ametridione, ametryn, amibuzin, amicarbazone,amicarthiazol, amidithion, amidoflumet, amidosulfuron, aminocarb,aminocyclopyrachlor, aminocyclopyrachlor-methyl,aminocyclopyrachlor-potassium, aminopyralid, aminopyralid-potassium,aminopyralid-tris(2-hydroxypropyl)ammonium, amiprofos-methyl,amiprophos, amisulbrom, amiton, amiton oxalate, amitraz, amitrole,ammonium sulfamate, ammonium α-naphthaleneacetate, amobam, ampropylfos,anabasine, ancymidol, anilazine, anilofos, anisuron, anthraquinone,antu, apholate, aramite, arsenous oxide, asomate, aspirin, asulam,asulam-potassium, asulam-sodium, athidathion, atraton, atrazine,aureofungin, aviglycine, aviglycine hydrochloride, azaconazole,azadirachtin, azafenidin, azamethiphos, azimsulfuron, azinphos-ethyl,azinphos-methyl, aziprotryne, azithiram, azobenzene, azocyclotin,azothoate, azoxystrobin, bachmedesh, barban, barium hexafluorosilicate,barium polysulfide, barthrin, BCPC, beflubutamid, benalaxyl,benalaxyl-M, benazolin, benazolin-dimethylammonium, benazolin-ethyl,benazolin-potassium, bencarbazone, benclothiaz, bendiocarb, benfluralin,benfuracarb, benfuresate, benodanil, benomyl, benoxacor, benoxafos,benquinox, bensulfuron, bensulfuron-methyl, bensulide, bensultap,bentaluron, bentazone, bentazone-sodium, benthiavalicarb,benthiavalicarb-isopropyl, benthiazole, bentranil, benzadox,benzadox-ammonium, benzalkonium chloride, benzamacril,benzamacril-isobutyl, benzamorf, benzfendizone, benzipram,benzobicyclon, benzofenap, benzofluor, benzohydroxamic acid,benzoximate, benzoylprop, benzoylprop-ethyl, benzthiazuron, benzylbenzoate, benzyladenine, berberine, berberine chloride, beta-cyfluthrin,beta-cypermethrin, bethoxazin, bicyclopyrone, bifenazate, bifenox,bifenthrin, bifujunzhi, bilanafos, bilanafos-sodium, binapacryl,bingqingxiao, bioallethrin, bioethanomethrin, biopermethrin,bioresmethrin, biphenyl, bisazir, bismerthiazol, bispyribac,bispyribac-sodium, bistrifluron, bitertanol, bithionol, bixafen,blasticidin-S, borax, Bordeaux mixture, boric acid, boscalid,brassinolide, brassinolide-ethyl, brevicomin, brodifacoum,brofenvalerate, brofluthrinate, bromacil, bromacil-lithium,bromacil-sodium, bromadiolone, bromethalin, bromethrin, bromfenvinfos,bromoacetamide, bromobonil, bromobutide, bromocyclen, bromo-DDT,bromofenoxim, bromophos, bromophos-ethyl, bromopropylate, bromothalonil,bromoxynil, bromoxynil butyrate, bromoxynil heptanoate, bromoxyniloctanoate, bromoxynil-potassium, brompyrazon, bromuconazole, bronopol,bucarpolate, bufencarb, buminafos, bupirimate, buprofezin, Burgundymixture, busulfan, butacarb, butachlor, butafenacil, butamifos,butathiofos, butenachlor, butethrin, buthidazole, buthiobate, buthiuron,butocarboxim, butonate, butopyronoxyl, butoxycarboxim, butralin,butroxydim, buturon, butylamine, butylate, cacodylic acid, cadusafos,cafenstrole, calcium arsenate, calcium chlorate, calcium cyanamide,calcium polysulfide, calvinphos, cambendichlor, camphechlor, camphor,captafol, captan, carbamorph, carbanolate, carbaryl, carbasulam,carbendazim, carbendazim benzenesulfonate, carbendazim sulfite,carbetamide, carbofuran, carbon disulfide, carbon tetrachloride,carbophenothion, carbosulfan, carboxazole, carboxide, carboxin,carfentrazone, carfentrazone-ethyl, carpropamid, cartap, cartaphydrochloride, carvacrol, carvone, CDEA, cellocidin, CEPC, ceralure,Cheshunt mixture, chinomethionat, chitosan, chlobenthiazone,chlomethoxyfen, chloralose, chloramben, chloramben-ammonium,chloramben-diolamine, chloramben-methyl, chloramben-methylammonium,chloramben-sodium, chloramine phosphorus, chloramphenicol,chloraniformethan, chloranil, chloranocryl, chlorantraniliprole,chlorazifop, chlorazifop-propargyl, chlorazine, chlorbenside,chlorbenzuron, chlorbicyclen, chlorbromuron, chlorbufam, chlordane,chlordecone, chlordimeform, chlordimeform hydrochloride,chlorempenthrin, chlorethoxyfos, chloreturon, chlorfenac,chlorfenac-ammonium, chlorfenac-sodium, chlorfenapyr, chlorfenazole,chlorfenethol, chlorfenprop, chlorfenson, chlorfensulphide,chlorfenvinphos, chlorfluazuron, chlorflurazole, chlorfluren,chlorfluren-methyl, chlorflurenol, chlorflurenol-methyl, chloridazon,chlorimuron, chlorimuron-ethyl, chlormephos, chlormequat, chlormequatchloride, chlornidine, chlornitrofen, chlorobenzilate,chlorodinitronaphthalenes, chloroform, chloromebuform, chloromethiuron,chloroneb, chlorophacinone, chlorophacinone-sodium, chloropicrin,chloropon, chloropropylate, chlorothalonil, chlorotoluron, chloroxuron,chloroxynil, chlorphonium, chlorphonium chloride, chlorphoxim,chlorprazophos, chlorprocarb, chlorpropham, chlorpyrifos,chlorpyrifos-methyl, chlorquinox, chlorsulfuron, chlorthal,chlorthal-dimethyl, chlorthal-monomethyl, chlorthiamid, chlorthiophos,chlozolinate, choline chloride, chromafenozide, cinerin I, cinerin II,cinerins, cinidon-ethyl, cinmethylin, cinosulfuron, ciobutide,cisanilide, cismethrin, clethodim, climbazole, cliodinate, clodinafop,clodinafop-propargyl, cloethocarb, clofencet, clofencet-potassium,clofentezine, clofibric acid, clofop, clofop-isobutyl, clomazone,clomeprop, cloprop, cloproxydim, clopyralid, clopyralid-methyl,clopyralid-olamine, clopyralid-potassium,clopyralid-tris(2-hydroxypropyl)ammonium, cloquintocet,cloquintocet-mexyl, cloransulam, cloransulam-methyl, closantel,clothianidin, clotrimazole, cloxyfonac, cloxyfonac-sodium, CMA,codlelure, colophonate, copper acetate, copper acetoarsenite, copperarsenate, copper carbonate, basic, copper hydroxide, copper naphthenate,copper oleate, copper oxychloride, copper silicate, copper sulfate,copper zinc chromate, coumachlor, coumafuryl, coumaphos, coumatetralyl,coumithoate, coumoxystrobin, CPMC, CPMF, CPPC, credazine, cresol,crimidine, crotamiton, crotoxyphos, crufomate, cryolite, cue-lure,cufraneb, cumyluron, cuprobam, cuprous oxide, curcumenol, cyanamide,cyanatryn, cyanazine, cyanofenphos, cyanophos, cyanthoate,cyantraniliprole, cyazofamid, cybutryne, cyclafuramid, cyclanilide,cyclethrin, cycloate, cycloheximide, cycloprate, cycloprothrin,cyclosulfamuron, cycloxydim, cycluron, cyenopyrafen, cyflufenamid,cyflumetofen, cyfluthrin, cyhalofop, cyhalofop-butyl, cyhalothrin,cyhexatin, cymiazole, cymiazole hydrochloride, cymoxanil, cyometrinil,cypendazole, cypermethrin, cyperquat, cyperquat chloride, cyphenothrin,cyprazine, cyprazole, cyproconazole, cyprodinil, cyprofuram, cypromid,cyprosulfamide, cyromazine, cythioate, daimuron, dalapon,dalapon-calcium, dalapon-magnesium, dalapon-sodium, daminozide,dayoutong, dazomet, dazomet-sodium, DBCP, d-camphor, DCIP, DCPTA, DDT,debacarb, decafentin, decathofuran, dehydroacetic acid, delachlor,deltamethrin, demephion, demephion-O, demephion-S, demeton,demeton-methyl, demeton-O, demeton-O-methyl, demeton-S,demeton-S-methyl, demeton-S-methylsulphon, desmedipham, desmetryn,d-fanshiluquebingjuzhi, diafenthiuron, dialifos, di-allate, diamidafos,diatomaceous earth, diazinon, dibutyl phthalate, dibutyl succinate,dicamba, dicamba-diglycolamine, dicamba-dimethylammonium,dicamba-diolamine, dicamba-isopropylammonium, dicamba-methyl,dicamba-olamine, dicamba-potassium, dicamba-sodium, dicamba-trolamine,dicapthon, dichlobenil, dichlofenthion, dichlofluanid, dichlone,dichloralurea, dichlorbenzuron, dichlorflurenol, dichlorflurenol-methyl,dichlormate, dichlormid, dichlorophen, dichlorprop,dichlorprop-2-ethylhexyl, dichlorprop-butotyl,dichlorprop-dimethylammonium, dichlorprop-ethylammonium,dichlorprop-isoctyl, dichlorprop-methyl, dichlorprop-P,dichlorprop-P-2-ethylhexyl, dichlorprop-P-dimethylammonium,dichlorprop-potassium, dichlorprop-sodium, dichlorvos, dichlozoline,diclobutrazol, diclocymet, diclofop, diclofop-methyl, diclomezine,diclomezine-sodium, dicloran, diclosulam, dicofol, dicoumarol, dicresyl,dicrotophos, dicyclanil, dicyclonon, dieldrin, dienochlor, diethamquat,diethamquat dichloride, diethatyl, diethatyl-ethyl, diethofencath,dietholate, diethyl pyrocarbonate, diethyltoluamide, difenacoum,difenoconazole, difenopenten, difenopenten-ethyl, difenoxuron,difenzoquat, difenzoquat metilsulfate, difethialone, diflovidazin,diflubenzuron, diflufenican, diflufenzopyr, diflufenzopyr-sodium,diflumetorim, dikegulac, dikegulac-sodium, dilor, dimatif, dimefluthrin,dimefox, dimefuron, dimepiperate, dimetachlone, dimetan, dimethacarb,dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimethipin,dimethirimol, dimethoate, dimethomorph, dimethrin, dimethyl carbate,dimethyl phthalate, dimethylvinphos, dimetilan, dimexano, dimidazon,dimoxystrobin, dinex, dinex-diclexine, dingjunezuo, diniconazole,diniconazole-M, dinitramine, dinobuton, dinocap, dinocap-4, dinocap-6,dinocton, dinofenate, dinopenton, dinoprop, dinosam, dinoseb, dinosebacetate, dinoseb-ammonium, dinoseb-diolamine, dinoseb-sodium,dinoseb-trolamine, dinosulfon, dinotefuran, dinoterb, dinoterb acetate,dinoterbon, diofenolan, dioxabenzofos, dioxacarb, dioxathion,diphacinone, diphacinone-sodium, diphenamid, diphenyl sulfone,diphenylamine, dipropalin, dipropetryn, dipyrithione, diquat, diquatdibromide, disparlure, disul, disulfiram, disulfoton, disul-sodium,ditalimfos, dithianon, dithicrofos, dithioether, dithiopyr, diuron,d-limonene, DMPA, DNOC, DNOC-ammonium, DNOC-potassium, DNOC-sodium,dodemorph, dodemorph acetate, dodemorph benzoate, dodicin, dodicinhydrochloride, dodicin-sodium, dodine, dofenapyn, dominicalure,doramectin, drazoxolon, DSMA, dufulin, EBEP, EBP, ecdysterone,edifenphos, eglinazine, eglinazine-ethyl, emamectin, emamectin benzoate,EMPC, empenthrin, endosulfan, endothal, endothal-diammonium,endothal-dipotassium, endothal-disodium, endothion, endrin,enestroburin, EPN, epocholeone, epofenonane, epoxiconazole,eprinomectin, epronaz, EPTC, ethon, ergocalciferol, erlujixiancaoan,esdépalléthrine, esfenvalerate, esprocarb, etacelasil, etaconazole,etaphos, etem, ethaboxam, ethachlor, ethalfluralin, ethametsulfuron,ethametsulfuron-methyl, ethaprochlor, ethephon, ethidimuron,ethiofencarb, ethiolate, ethion, ethiozin, ethiprole, ethirimol,ethoate-methyl, ethofumesate, ethohexadiol, ethoprophos, ethoxyfen,ethoxyfen-ethyl, ethoxyquin, ethoxysulfuron, ethychlozate, ethylformate, ethyl α-naphthaleneacetate, ethyl-DDD, ethylene, ethylenedibromide, ethylene dichloride, ethylene oxide, ethylicin, ethylmercury2,3-dihydroxypropyl mercaptide, ethylmercury acetate, ethylmercurybromide, ethylmercury chloride, ethylmercury phosphate, etinofen,etnipromid, etobenzanid, etofenprox, etoxazole, etridiazole, etrimfos,eugenol, EXD, famoxadone, famphur, fenamidone, fenaminosulf, fenamiphos,fenapanil, fenarimol, fenasulam, fenazaflor, fenazaquin, fenbuconazole,fenbutatin oxide, fenchlorazole, fenchlorazole-ethyl, fenchlorphos,fenclorim, fenethacarb, fenfluthrin, fenfuram, fenhexamid, fenitropan,fenitrothion, fenjuntong, fenobucarb, fenoprop, fenoprop-3-butoxypropyl,fenoprop-butometyl, fenoprop-butotyl, fenoprop-butyl, fenoprop-isoctyl,fenoprop-methyl, fenoprop-potassium, fenothiocarb, fenoxacrim,fenoxanil, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P,fenoxaprop-P-ethyl, fenoxasulfone, fenoxycarb, fenpiclonil,fenpirithrin, fenpropathrin, fenpropidin, fenpropimorph, fenpyrazamine,fenpyroximate, fenridazon, fenridazon-potassium, fenridazon-propyl,fenson, fensulfothion, fenteracol, fenthiaprop, fenthiaprop-ethyl,fenthion, fenthion-ethyl, fentin, fentin acetate, fentin chloride,fentin hydroxide, fentrazamide, fentrifanil, fenuron, fenuron TCA,fenvalerate, ferbam, ferimzone, ferrous sulfate, fipronil, flamprop,flamprop-isopropyl, flamprop-M, flamprop-methyl, flamprop-M-isopropyl,flamprop-M-methyl, flazasulfuron, flocoumafen, flometoquin, flonicamid,florasulam, fluacrypyrim, fluazifop, fluazifop-butyl, fluazifop-methyl,fluazifop-P, fluazifop-P-butyl, fluazinam, fluazolate, fluazuron,flubendiamide, flubenzimine, flucarbazone, flucarbazone-sodium,flucetosulfuron, fluchloralin, flucofuron, flucycloxuron, flucythrinate,fludioxonil, fluenetil, fluensulfone, flufenacet, flufenerim,flufenican, flufenoxuron, flufenprox, flufenpyr, flufenpyr-ethyl,flufiprole, flumethrin, flumetover, flumetmlin, flumetsulam, flumezin,flumiclorac, flumiclorac-pentyl, flumioxazin, flumipropyn, flumorph,fluometuron, fluopicolide, fluopyram, fluorbenside, fluoridamid,fluoroacetamide, fluorodifen, fluoroglycofen, fluoroglycofen-ethyl,fluoroimide, fluoromidine, fluoronitrofen, fluothiuron, fluotrimazole,fluoxastrobin, flupoxam, flupropacil, flupropadine, flupropanate,flupropanate-sodium, flupyradifurone, flupyrsulfuron,flupyrsulfuron-methyl, flupyrsulfuron-methyl-sodium, fluquinconazole,flurazole, flurenol, flurenol-butyl, flurenol-methyl, fluridone,flurochloridone, fluroxypyr, fluroxypyr-butometyl, fluroxypyr-meptyl,flurprimidol, flursulamid, flurtamone, flusilazole, flusulfamide,fluthiacet, fluthiacet-methyl, flutianil, flutolanil, flutriafol,fluvalinate, fluxapyroxad, fluxofenim, folpet, fomesafen,fomesafen-sodium, fonofos, foramsulfuron, forchlorfenuron, formaldehyde,formetanate, formetanate hydrochloride, formothion, formparanate,formparanate hydrochloride, fosamine, fosamine-ammonium, fosetyl,fosetyl-aluminium, fosmethilan, fospirate, fosthiazate, fosthietan,frontalin, fuberidazole, fucaojing, fucaomi, funaihecaoling,fuphenthiourea, furalane, furalaxyl, furamethrin, furametpyr,furathiocarb, furcarbanil, furconazole, furconazole-cis, furethrin,furfural, furilazole, furmecyclox, furophanate, furyloxyfen,gamma-cyhalothrin, gamma-HCH, genit, gibberellic acid, gibberellins,gliftor, glufosinate, glufosinate-ammonium, glufosinate-P,glufosinate-P-ammonium, glufosinate-P-sodium, glyodin, glyoxime,glyphosate, glyphosate-diammonium, glyphosate-dimethylammonium,glyphosate-isopropylammonium, glyphosate-monoammonium,glyphosate-potassium, glyphosate-sesquisodium, glyphosate-trimesium,glyphosine, gossyplure, grandlure, griseofulvin, guazatine, guazatineacetates, halacrinate, halfenprox, halofenozide, halosafen,halosulfuron, halosulfuron-methyl, haloxydine, haloxyfop,haloxyfop-etotyl, haloxyfop-methyl, haloxyfop-P, haloxyfop-P-etotyl,haloxyfop-P-methyl, haloxyfop-sodium, HCH, hemel, hempa, HEOD,heptachlor, heptenophos, heptopargil, heterophos, hexachloroacetone,hexachlorobenzene, hexachlorobutadiene, hexachlorophene, hexaconazole,hexaflumuron, hexaflurate, hexalure, hexamide, hexazinone, hexylthiofos,hexythiazox, HHDN, holosulf, huancaiwo, huangcaoling, huanjunzuo,hydramethylnon, hydrargaphen, hydrated lime, hydrogen cyanide,hydroprene, hymexazol, hyquincarb, IAA, IBA, icaridin, imazalil,imazalil nitrate, imazalil sulfate, imazamethabenz,imazamethabenz-methyl, imazamox, imazamox-ammonium, imazapic,imazapic-ammonium, imazapyr, imazapyr-isopropylammonium, imazaquin,imazaquin-ammonium, imazaquin-methyl, imazaquin-sodium, imazethapyr,imazethapyr-ammonium, imazosulfuron, imibenconazole, imicyafos,imidacloprid, imidaclothiz, iminoctadine, iminoctadine triacetate,iminoctadine trialbesilate, imiprothrin, inabenfide, indanofan,indaziflam, indoxacath, inezin, iodobonil, iodocarb, iodomethane,iodosulfuron, iodosulfuron-methyl, iodosulfuron-methyl-sodium,iofensulfuron, iofensulfuron-sodium, ioxynil, ioxynil octanoate,ioxynil-lithium, ioxynil-sodium, ipazine, ipconazole, ipfencarbazone,iprobenfos, iprodione, iprovalicarb, iprymidam, ipsdienol, ipsenol,IPSP, isamidofos, isazofos, isobenzan, isocarbamid, isocarbophos,isocil, isodrin, isofenphos, isofenphos-methyl, isolan, isomethiozin,isonoruron, isopolinate, isoprocarb, isopropalin, isoprothiolane,isoproturon, isopyrazam, isopyrimol, isothioate, isotianil, isouron,isovaledione, isoxaben, isoxachlortole, isoxadifen, isoxadifen-ethyl,isoxaflutole, isoxapyrifop, isoxathion, ivermectin, izopamfos,japonilure, japothrins, jasmolin I, jasmolin II, jasmonic acid,jiahuangchongzong, jiajizengxiaolin, jiaxiangjunzhi, jiecaowan,jiecaoxi, jodfenphos, juvenile hormone I, juvenile hormone II, juvenilehormone III, kadethrin, karbutilate, karetazan, karetazan-potassium,kasugamycin, kasugamycin hydrochloride, kejunlin, kelevan, ketospiradox,ketospiradox-potassium, kinetin, kinoprene, kresoxim-methyl, kuicaoxi,lactofen, lambda-cyhalothrin, latilure, lead arsenate, lenacil,lepimectin, leptophos, lindane, lineatin, linuron, lirimfos, litlure,looplure, lufenuron, lvdingjunzhi, lvxiancaolin, lythidathion, MAA,malathion, maleic hydrazide, malonoben, maltodextrin, MAMA, mancopper,mancozeb, mandipropamid, maneb, matrine, mazidox, MCPA,MCPA-2-ethylhexyl, MCPA-butotyl, MCPA-butyl, MCPA-dimethylammonium,MCPA-diolamine, MCPA-ethyl, MCPA-isobutyl, MCPA-isoctyl, MCPA-isopropyl,MCPA-methyl, MCPA-olamine, MCPA-potassium, MCPA-sodium, MCPA-thioethyl,MCPA-trolamine, MCPB, MCPB-ethyl, MCPB-methyl, MCPB-sodium, mebenil,mecarbam, mecarbinzid, mecarphon, mecoprop, mecoprop-2-ethylhexyl,mecoprop-dimethylammonium, mecoprop-diolamine, mecoprop-ethadyl,mecoprop-isoctyl, mecoprop-methyl, mecoprop-P, mecoprop-P-2-ethylhexyl,mecoprop-P-dimethylammonium, mecoprop-P-isobutyl, mecoprop-potassium,mecoprop-P-potassium, mecoprop-sodium, mecoprop-trolamine, medimeform,medinoterb, medinoterb acetate, medlure, mefenacet, mefenpyr,mefenpyr-diethyl, mefluidide, mefluidide-diolamine,mefluidide-potassium, megatomoic acid, menazon, mepanipyrim,meperfluthrin, mephenate, mephosfolan, mepiquat, mepiquat chloride,mepiquat pentaborate, mepronil, meptyldinocap, mercuric chloride,mercuric oxide, mercurous chloride, merphos, mesoprazine, mesosulfuron,mesosulfuron-methyl, mesotrione, mesulfen, mesulfenfos, metaflumizone,metalaxyl, metalaxyl-M, metaldehyde, metam, metam-ammonium, metamifop,metamitron, metam-potassium, metam-sodium, metazachlor, metazosulfuron,metazoxolon, metconazole, metepa, metflurazon, methabenzthiazuron,methacrifos, methalpropalin, methamidophos, methasulfocarb, methazole,methfuroxam, methidathion, methiobencarb, methiocarb,methiopyrisulfuron, methiotepa, methiozolin, methiuron, methocrotophos,methometon, methomyl, methoprene, methoprotryne, methoquin-butyl,methothrin, methoxychlor, methoxyfenozide, methoxyphenone, methylapholate, methyl bromide, methyl eugenol, methyl iodide, methylisothiocyanate, methylacetophos, methylchloroform, methyldymron,methylene chloride, methylmercury benzoate, methylmercury dicyandiamide,methylmercury pentachlorophenoxide, methylneodecanamide, metiram,metobenzuron, metobromuron, metofluthrin, metolachlor, metolcarb,metominostrobin, metosulam, metoxadiazone, metoxuron, metrafenone,metribuzin, metsulfovax, metsulfuron, metsulfuron-methyl, mevinphos,mexacarbate, mieshuan, milbemectin, milbemycin oxime, milneb, mipafox,mirex, MNAF, moguchun, molinate, molosultap, monalide, monisouron,monochloroacetic acid, monocrotophos, monolinuron, monosulfuron,monosulfuron-ester, monuron, monuron TCA, morfamquat, morfamquatdichloride, moroxydine, moroxydine hydrochloride, morphothion, morzid,moxidectin, MSMA, muscalure, myclobutanil, myclozolin,N-(ethylmercury)-p-toluenesulphonanilide, nabam, naftalofos, naled,naphthalene, naphthaleneacetamide, naphthalic anhydride, naphthoxyaceticacids, naproanilide, napropamide, naptalam, naptalam-sodium, natamycin,neburon, niclosamide, niclosamide-olamine, nicosulfuron, nicotine,nifluridide, nipyraclofen, nitenpyram, nithiazine, nitralin, nitrapyrin,nitrilacarb, nitrofen, nitrofluorfen, nitrostyrene, nitrothal-isopropyl,norbormide, norflurazon, nornicotine, noruron, novaluron, noviflumuron,nuarimol, OCH, octachlorodipropyl ether, octhilinone, ofurace,omethoate, orbencarb, orfralure, ortho-dichlorobenzene, orthosulfamuron,oryctalure, orysastrobin, oryzalin, osthol, ostramone, oxabetrinil,oxadiargyl, oxadiazon, oxadixyl, oxamate, oxamyl, oxapyrazon,oxapyrazon-dimolamine, oxapyrazon-sodium, oxasulfuron, oxaziclomefone,oxine-copper, oxolinic acid, oxpoconazole, oxpoconazole fumarate,oxycarboxin, oxydemeton-methyl, oxydeprofos, oxydisulfoton, oxyfluorfen,oxymatrine, oxytetracycline, oxytetracycline hydrochloride,paclobutrazol, paichongding, para-dichlorobenzene, parafluron, paraquat,paraquat dichloride, paraquat dimetilsulfate, parathion,parathion-methyl, parinol, pebulate, pefurazoate, pelargonic acid,penconazole, pencycuron, pendimethalin, penflufen, penfluron,penoxsulam, pentachlorophenol, pentanochlor, penthiopyrad, pentmethrin,pentoxazone, perfluidone, permethrin, pethoxamid, phenamacril, phenazineoxide, phenisopham, phenkapton, phenmedipham, phenmedipham-ethyl,phenobenzuron, phenothrin, phenproxide, phenthoate, phenylmercuriurea,phenylmercury acetate, phenylmercury chloride, phenylmercury derivativeof pyrocatechol, phenylmercury nitrate, phenylmercury salicylate,phorate, phosacetim, phosalone, phosdiphen, phosfolan, phosfolan-methyl,phosglycin, phosmet, phosnichlor, phosphamidon, phosphine, phosphocarb,phosphorus, phostin, phoxim, phoxim-methyl, phthalide, picloram,picloram-2-ethylhexyl, picloram-isoctyl, picloram-methyl,picloram-olamine, picloram-potassium, picloram-triethylammonium,picloram-tris(2-hydroxypropyl)ammonium, picolinafen, picoxystrobin,pindone, pindone-sodium, pinoxaden, piperalin, piperonyl butoxide,piperonyl cyclonene, piperophos, piproctanyl, piproctanyl bromide,piprotal, pirimetaphos, pirimicarb, pirimioxyphos, pirimiphos-ethyl,pirimiphos-methyl, plifenate, polycarbamate, polyoxins, polyoxorim,polyoxorim-zinc, polythialan, potassium arsenite, potassium azide,potassium cyanate, potassium gibberellate, potassium naphthenate,potassium polysulfide, potassium thiocyanate, potassiumα-naphthaleneacetate, pp′-DDT, prallethrin, precocene I, precocene II,precocene III, pretilachlor, primidophos, primisulfuron,primisulfuron-methyl, probenazole, prochloraz, prochloraz-manganese,proclonol, procyazine, procymidone, prodiamine, profenofos, profluazol,profluralin, profluthrin, profoxydim, proglinazine, proglinazine-ethyl,prohexadione, prohexadione-calcium, prohydrojasmon, promacyl, promecarb,prometon, prometryn, promurit, propachlor, propamidine, propamidinedihydrochloride, propamocarb, propamocarb hydrochloride, propanil,propaphos, propaquizafop, propargite, proparthrin, propazine,propetamphos, propham, propiconazole, propineb, propisochlor, propoxur,propoxycarbazone, propoxycarbazone-sodium, propyl isome,propyrisulfuron, propyzamide, proquinazid, prosuler, prosulfalin,prosulfocarb, prosulfuron, prothidathion, prothiocarb, prothiocarbhydrochloride, prothioconazole, prothiofos, prothoate, protrifenbute,proxan, proxan-sodium, prynachlor, pydanon, pymetrozine, pyracarbolid,pyraclofos, pyraclonil, pyraclostrobin, pyraflufen, pyraflufen-ethyl,pyrafluprole, pyramat, pyrametostrobin, pyraoxystrobin, pyrasulfotole,pyrazolynate, pyrazophos, pyrazosulfuron, pyrazosulfuron-ethyl,pyrazothion, pyrazoxyfen, pyresmethrin, pyrethrin I, pyrethrin II,pyrethrins, pyribambenz-isopropyl, pyribambenz-propyl, pyribencarb,pyribenzoxim, pyributicarb, pyriclor, pyridaben, pyridafol, pyridalyl,pyridaphenthion, pyridate, pyridinitril, pyrifenox, pyrifluquinazon,pyriftalid, pyrimethanil, pyrimidifen, pyriminobac, pyriminobac-methyl,pyrimisulfan, pyrimitate, pyrinuron, pyriofenone, pyriprole,pyripropanol, pyriproxyfen, pyrithiobac, pyrithiobac-sodium, pyrolan,pyroquilon, pyroxasulfone, pyroxsulam, pyroxychlor, pyroxyfur, quassia,quinacetol, quinacetol sulfate, quinalphos, quinalphos-methyl,quinazamid, quinclorac, quinconazole, quinmerac, quinoclamine,quinonamid, quinothion, quinoxyfen, quintiofos, quintozene, quizalofop,quizalofop-ethyl, quizalofop-P, quizalofop-P-ethyl,quizalofop-P-tefuryl, quwenzhi, quyingding, rabenzazole, rafoxanide,rebemide, resmethrin, rhodethanil, rhodojaponin-III, ribavirin,nmsulfuron, rotenone, ryania, saflufenacil, saijunmao, saisentong,salicylanilide, sanguinarine, santonin, schradan, scilliroside,sebuthylazine, secbumeton, sedaxane, selamectin, semiamitraz,semiamitraz chloride, sesamex, sesamolin, sethoxydim, shuangjiaancaolin,siduron, siglure, silafluofen, silatrane, silica gel, silthiofam,simazine, simeconazole, simeton, simetryn, sintofen, SMA, S-metolachlor,sodium arsenite, sodium azide, sodium chlorate, sodium fluoride, sodiumfluoroacetate, sodium hexafluorosilicate, sodium naphthenate, sodiumorthophenylphenoxide, sodium pentachlorophenoxide, sodium polysulfide,sodium thiocyanate, sodium α-naphthaleneacetate, sophamide, spinetoram,spinosad, spirodiclofen, spiromesifen, spirotetramat, spiroxamine,streptomycin, streptomycin sesquisulfate, strychnine, sulcatol,sulcofuron, sulcofuron-sodium, sulcotrione, sulfallate, sulfentrazone,sulfiram, sulfluramid, sulfometuron, sulfometuron-methyl, sulfosulfuron,sulfotep, sulfoxaflor, sulfoxide, sulfoxime, sulfur, sulfuric acid,sulfuryl fluoride, sulglycapin, sulprofos, sultropen, swep,tau-fluvalinate, tavron, tazimcarb, TCA, TCA-ammonium, TCA-calcium,TCA-ethadyl, TCA-magnesium, TCA-sodium, TDE, tebuconazole, tebufenozide,tebufenpyrad, tebufloquin, tebupirimfos, tebutam, tebuthiuron,tecloftalam, tecnazene, tecoram, teflubenzuron, tefluthrin,tefuryltrione, tembotrione, temephos, tepa, TEPP, tepraloxydim,terallethrin, terbacil, terbucarb, terbuchlor, terbufos, terbumeton,terbuthylazine, terbutryn, tetcyclacis, tetrachloroethane,tetrachlorvinphos, tetraconazole, tetradifon, tetrafluron, tetramethrin,tetramethylfluthrin, tetramine, tetranactin, tetrasul, thallium sulfate,thenylchlor, theta-cypermethrin, thiabendazole, thiacloprid,thiadifluor, thiamethoxam, thiapronil, thiazafluron, thiazopyr,thicrofos, thicyofen, thidiazimin, thidiazuron, thiencarbazone,thiencarbazone-methyl, thifensulfuron, thifensulfuron-methyl,thifluzamide, thiobencarb, thiocarboxime, thiochlorfenphim, thiocyclam,thiocyclam hydrochloride, thiocyclam oxalate, thiodiazole-copper,thiodicarb, thiofanox, thiofluoximate, thiohempa, thiomersal, thiometon,thionazin, thiophanate, thiophanate-methyl, thioquinox,thiosemicarbazide, thiosultap, thiosultap-diammonium,thiosultap-disodium, thiosultap-monosodium, thiotepa, thiram,thuringiensin, tiadinil, tiaojiean, tiocarbazil, tioclorim, tioxymid,tirpate, tolclofos-methyl, tolfenpyrad, tolylfluanid, tolylmercuryacetate, topramezone, tralkoxydim, tralocythrin, tralomethrin,tralopyril, tmnsfluthrin, tmnspermethrin, tretamine, triacontanol,triadimefon, triadimenol, triafamone, tri-allate, triamiphos,triapenthenol, triarathene, triarimol, triasulfuron, triazamate,triazbutil, triaziflam, triazophos, triazoxide, tribenuron,tribenuron-methyl, tribufos, tributyltin oxide, tricamba, trichlamide,trichlorfon, trichlormetaphos-3, trichloronat, triclopyr,triclopyr-butotyl, triclopyr-ethyl, triclopyr-triethylammonium,tricyclazole, tridemorph, tridiphane, trietazine, trifenmorph,trifenofos, trifloxystrobin, trifloxysulfuron, trifloxysulfuron-sodium,triflumizole, triflumuron, trifluralin, triflusulfuron,triflusulfuron-methyl, trifop, trifop-methyl, trifopsime, triforine,trihydroxytriazine, trimedlure, trimethacarb, trimeturon, trinexapac,trinexapac-ethyl, triprene, tripropindan, triptolide, tritac,triticonazole, tritosulfuron, trunc-call, uniconazole, uniconazole-P,urbacide, uredepa, valerate, validamycin, valifenalate, valone,vamidothion, vangard, vaniliprole, vernolate, vinclozolin, warfarin,warfarin-potassium, warfarin-sodium, xiaochongliulin, xinjunan,xiwojunan, XMC, xylachlor, xylenols, xylylcarb, yishijing, zarilamid,zeatin, zengxiaoan, zeta-cypermethrin, zinc naphthenate, zinc phosphide,zinc thiazole, zineb, ziram, zolaprofos, zoxamide, zuomihuanglong,α-chlorohydrin, α-ecdysone, α-multistriatin, and α-naphthaleneaceticacid.
 17. The process of claim 1, wherein the pesticidal compositionfurther comprising a biopesticide.
 18. The process of claim 1, whereinthe pesticidal composition further comprises at least one of thefollowing compounds: (a)3-(4-chloro-2,6-dimethylphenyl)-4-hydroxy-8-oxa-1-azaspiro[4,5]dec-3-en-2-one;(b)3-(4′-chloro-2,4-dimethyl[1,1′-biphenyl]-3-yl)-4-hydroxy-8-oxa-1-azaspiro[4,5]dec-3-en-2-one;(c) 4-[[(6-chloro-3-pyridinyl)methyl]methylamino]-2(5H)-furanone; (d)4-[[(6-chloro-3-pyridinyl)methyl]cyclopropylamino]-2(5H)-furanone; (e)3-chloro-N2-[(1S)-1-methyl-2-(methylsulfonyl)ethyl]-N1-[2-methyl-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-1,2-benzenedicarboxamide;(f) 2-cyano-N-ethyl-4-fluoro-3-methoxy-benenesulfonamide; (g)2-cyano-N-ethyl-3-methoxy-benzenesulfonamide; (h)2-cyano-3-difluoromethoxy-N-ethyl-4-fluoro-benzenesulfonamide; (i)2-cyano-3-fluoromethoxy-N-ethyl-benzenesulfonamide; (j)2-cyano-6-fluoro-3-methoxy-N,N-dimethyl-benzenesulfonamide; (k)2-cyano-N-ethyl-6-fluoro-3-methoxy-N-methyl-benzenesulfonamide; (l)2-cyano-3-difluoromethoxy-N,N-dimethylbenzenesulfon-amide; (m)3-(difluoromethyl)-N-[2-(3,3-dimethylbutyl)phenyl]-1-methyl-1H-pyrazole-4-carboxamide;(n)N-ethyl-2,2-dimethylpropionamide-2-(2,6-dichloro-α,α,α-trifluoro-p-tolyl)hydrazone;(o)N-ethyl-2,2-dichloro-1-methylcyclopropane-carboxamide-2-(2,6-dichloro-α,α,α-trifluoro-p-tolyl)hydrazonenicotine; (p)O-{(E-)-[2-(4-chloro-phenyl)-2-cyano-1-(2-trifluoromethylphenyl)-vinyl]}S-methylthiocarbonate; (q)(E)-N1-[(2-chloro-1,3-thiazol-5-ylmethyl)]-N2-cyano-N1-methylacetamidine;(r)1-(6-chloropyridin-3-ylmethyl)-7-methyl-8-nitro-1,2,3,5,6,7-hexahydro-imidazo[1,2-a]pyridin-5-ol;(s) 4-[4-chlorophenyl-(2-butylidine-hydrazono)methyl)]phenyl mesylate;and (t)N-ethyl-2,2-dichloro-1-methylcyclopropanecarboxamide-2-(2,6-dichloro-α,α,α-trifluoro-p-tolyl)hydrazone.19. The process of claim 1, wherein the pesticidal composition furthercomprises a compound having one or more of the following modes ofaction: acetylcholinesterase inhibitor; sodium channel modulator; chitinbiosynthesis inhibitor; GABA and glutamate-gated chloride channelantagonist; GABA and glutamate-gated chloride channel agonist;acetylcholine receptor agonist; acetylcholine receptor antagonist; MET Iinhibitor; Mg-stimulated ATPase inhibitor; nicotinic acetylcholinereceptor; Midgut membrane disrupter; oxidative phosphorylationdisrupter, and ryanodine receptor (RyRs).
 20. The process of to claim 1,wherein the pesticidal composition is encapsulated inside, or placed onthe surface of, a capsule.